WO2014193050A1

WO2014193050A1 - Continuous solid-state polymerization device and method

Info

Publication number: WO2014193050A1
Application number: PCT/KR2013/009439
Authority: WO
Inventors: 박경균; 임상균; 전민아; 배신효; 유형국
Original assignee: 제일모직 주식회사
Priority date: 2013-05-31
Filing date: 2013-10-22
Publication date: 2014-12-04

Abstract

A continuous solid-state polymerization device of the present invention comprises: a feeder for continuously injecting a prepolymer; a horizontal reactor, connected through a first connection part to the feeder, for receiving the prepolymer from the feeder and performing a solid-state polymerization, the reactor itself being rotated; a chamber, connected through a second connection part to the horizontal reactor, for receiving and discharging a polymer, of which the solid-state polymerization has been completed, discharged from the horizontal reactor; and a sealing member for sealing the first connection part and the second connection part, wherein the feeder, the horizontal reactor and the chamber are in a vacuum state. The continuous solid-state polymerization prevents formation of a congested section of a prepolymer, and can continuously perform solid-state polymerization in a vacuum state without an inert gas.

Description

Continuous solid state polymerization apparatus and method

The present invention relates to a continuous solid state polymerization apparatus and method. More specifically, the present invention relates to a continuous solid phase polymerization apparatus and method which prevents the formation of stagnant sections of the prepolymer and enables continuous solid phase polymerization in a vacuum without an inert gas.

Recently, polymer (polymer) compositions having high heat resistance characteristics have been widely used in automobile parts, electrical appliances, mechanical parts, beverage containers, fibers, films, tire cords, and the like. Examples of the polymer include aliphatic polyamide polymers such as nylon 66 and nylon 6, aromatic polyamide polymers (high heat resistant nylon resin) such as nylon 6T, nylon 9T, nylon 10T, and nylon 12T, and polyethylene terephthalate (PET) resins. Polyester resin, polycarbonate (PC) resin, etc. can be illustrated.

Usually, in order to improve the high heat resistance and high impact characteristic of a polymer, it is necessary to raise the intrinsic viscosity (IV) of a polymer. For example, as a method for obtaining a polymer having a high intrinsic viscosity of about 0.5 dL / g or more, a condensation polymerization process of a molten resin called a melting process may be performed.

However, this melting process results in high shear during polycondensation and transfer due to the high viscosity of the polymer (especially the crystalline polymer), which may result in decomposition of the product. In order to solve this problem, during the melting process, the temperature of the polymer should be operated and produced by raising the temperature higher than the melting temperature. Therefore, it is not economical due to the enormous energy consumption, especially in the high heat resistant resin having a high melting temperature. In addition, the polymer may be carbonized in the long term operation so that a large amount of contamination may be included in the final product, and the product may be discolored and may not be used in a product requiring high whiteness.

A commonly used technique to solve this problem is solid-state polymerization (SSP). Conventional solid phase polymerization includes a process in which an amorphous polymer chip, a prepolymer, or the like is introduced into a solid phase polymerization reactor and heated for several hours to several tens of hours while circulating and supplying an inert gas.

As the inert gas, nitrogen heated above the glass transition temperature of the polymer and below the melting temperature, for example, in the range of about 130 to about 250 ° C, is mainly used. The reason why the inert gas is used for the solid phase polymerization is that if an active gas such as oxygen is present in the system in which the polymerization is carried out, some products may cause serious yellowing and browning problems as polymerization proceeds at a high temperature. to be. That is, by circulating the inert gas in the reactor, the inlet of the active gas can be minimized, and reaction by-products such as water, aldehyde, glycol, and phenol generated in the process can be discharged together. However, when the by-products are recycled to the solid-phase polymerization reactor, the purity of the circulating inert gas gradually decreases, and as a result, the polymer may discolor, or the reaction rate may decrease due to the high by-product concentration or the polymerization may be reversed. Can be. Therefore, the inert gas must remove by-products before re-entry. As such, the conventional solid phase polymerization method requires a lot of energy and cost in order to remove by-products such as water contained in an inert gas stream and maintain purity, which is disadvantageous in that it is not economical.

Conventional batch solid phase polymerization reaction equipment is equipped with a rotary blade on top of a vertical reactor, and a prepolymer is introduced by utilizing a fixed reactor that performs a reaction while stirring and a reactor that is conical in both a phase and a bottom. Thereafter, there is a tumbler method (Japanese Patent Laid-Open No. JPA2001-270940, etc.) which proceeds while sealing and rotating the entire reactor body in a vacuum state.

In addition, the conventional continuous solid-phase polymerization equipment is a hopper type (International Patent Publication No. WO1998-023666, etc.) and a horizontal circular reactor system (Japanese Patent Laid-Open No. 10-87821, etc.). The hopper type uses a vertical reactor having a cylindrical upper part and a bottom of a reverse conical shape, injects a prepolymer to the upper part, and simultaneously inputs an inert gas heated near the bottom of the inverse conical lower part of the reactor to the floor. The final product (polymer) is discharged and the inert gas containing impurities generated during the reaction is discharged upwards. The horizontal circular reactor system uses a horizontal circular reactor having a screw or disk-shaped stirring blade inside, and inputs a prepolymer toward the inlet, and simultaneously mixes by using a stirring blade while introducing a heated inert gas. The polymer is discharged toward the outlet opposite the inlet, and the inert gas containing impurities is discharged to the upper side of the reactor outlet.

Batch reaction equipment can maintain a uniform intrinsic viscosity (IV) because the thermal history of the prepolymer can be maintained equal to that of the continuous reaction equipment, but the production per batch lot is small, and the cycle time ) And long temperature and cooling process must be repeated for the reaction, so the energy cost is high and the cost of the product increases.

The continuous reaction plant is more stable than the batch type and has a short cycle time, so it has high lot productivity, and can be produced in a small sized plant, thereby reducing investment cost, energy loss, and lowering product cost. However, the molecular weight distribution can be somewhat wider than the batch type, and thus, when molding a final product, the cycle time required for one molding can be increased, thereby reducing the productivity of the molded product. In addition, in the case of a horizontal reactor in which the reactor body is fixed and the stirring blade is rotated, an empty space must exist between the tip portion of the stirring blade tip and the inner wall of the reactor during solid phase polymerization. However, a stagnant zone in which the polymer is hardly flown in the space may be formed, which may result in deterioration of product quality due to generation of contamination and the like, and particle size due to pulverization of the prepolymer. It can cause change. In addition, in the continuous type, inert gas is generally used because it is difficult to continuously supply / discharge raw materials in a vacuum state, but the heating and cooling of the gas must be repeated, and a separate inert gas is needed to recover only pure inert gas from which by-products are removed. Purification process is required. For this reason, there is a disadvantage that the energy efficiency is not good compared to the rotary batch solid-state polymerization reactor.

Therefore, it is necessary to develop a continuous solid-state polymerization apparatus (reactor) capable of preventing the formation of stagnant sections of the prepolymer and reacting in a vacuum state.

It is an object of the present invention to provide a continuous solid phase polymerization apparatus and method capable of preventing the formation of stagnant sections of the prepolymer.

It is another object of the present invention to provide an economical continuous solid phase polymerization apparatus and method capable of continuously solid phase polymerizing in a vacuum without the use of an inert gas.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the invention relates to a continuous solid state polymerization apparatus. The continuous solid-state polymerization apparatus comprises a feeder for continuously input the prepolymer; A horizontal reactor connected to the feeder through a first connection part to receive a prepolymer from the feeder to perform solid phase polymerization, and to rotate the reactor itself; And a chamber connected to the horizontal reactor via a second connection to receive and discharge the polymer that has undergone solid phase polymerization discharged from the horizontal reactor, wherein the feeder, the horizontal reactor, and the chamber are in a vacuum state. It is characterized by.

In an embodiment, the continuous solid-state polymerization apparatus may include a sealing member for preventing the leakage and inflow of gas and liquid in the first connection portion and the second connection portion.

Preferably, the sealing member may be a magnetic fluid seal.

In an embodiment, a vacuum pump can be connected to the chamber.

In embodiments, a vacuum pump may be further connected to the feeder.

In embodiments, the transverse reactor may include a preheating section, a heating section, and a cooling section.

In an embodiment, the continuous solid phase polymerization apparatus may include a first hopper to which a prepolymer is introduced from the outside and maintains atmospheric pressure; And a second hopper connected to the first hopper to discharge the prepolymer discharged from the first hopper at atmospheric pressure, and introducing the prepolymer into the feeder in a vacuum state.

In embodiments, the continuous solid-state polymerization device, the polymer discharged from the chamber in the vacuum state connected to the chamber is introduced, it may further include a third hopper for discharging the polymer to the outside at atmospheric pressure. .

In embodiments, the prepolymer may have an intrinsic viscosity (IV) of about 0.09 to about 0.49 dL / g.

In embodiments, the polymer having completed the solid state polymerization may have an intrinsic viscosity (IV) of about 0.5 to about 1.5 dL / g.

Another aspect of the invention relates to a continuous solid phase polymerization method. The continuous solid phase polymerization method is a solid phase polymerization method using a continuous solid phase polymerization apparatus, the step of introducing a prepolymer into the feeder; Solid-phase polymerization of the prepolymer introduced in the horizontal reactor; And discharging the solid phase polymerized polymer into the chamber, wherein the steps are performed continuously.

In embodiments, the solid phase polymerization may be carried out under a pressure of about 0.1 to about 100 torr.

The present invention has the effect of providing an economical continuous solid phase polymerization apparatus and method capable of preventing the formation of stagnant sections of the prepolymer and capable of continuously solid phase polymerizing in a vacuum without the use of an inert gas.

1 is a schematic diagram of a continuous solid-state polymerization apparatus according to an embodiment of the present invention.

2 is a schematic diagram of a continuous solid-state polymerization apparatus according to another embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, the present invention will be described in detail.

1 is a schematic diagram of a continuous solid-state polymerization apparatus according to an embodiment of the present invention. As shown in Figure 1, the continuous solid-state polymerization apparatus according to the present invention, the feeder 10 for continuously input the prepolymer, is connected to the feeder 10 via a first connection, the feeder 10 Solid phase polymerization is carried out by accommodating the prepolymer, and is connected to the horizontal reactor 20 in which the reactor itself rotates, and connected to the horizontal reactor 20 through a second connection, and the solid phase discharged from the horizontal reactor 20. It comprises a chamber 30 for receiving and discharging the polymer is completed, the feeder 10, the horizontal reactor 20, and the chamber 30 is characterized in that the vacuum state.

In one embodiment, the continuous solid-state polymerization device is a first sealing member 40 to prevent the leakage and inflow of gas and liquid in the first connection portion and the second connection portion in order to maintain a vacuum state And surround the second connection portion.

In the present invention, the vacuum state refers to a low pressure or a reduced pressure lower than the normal pressure (about 760 torr), and may be, for example, about 0.1 to about 100 torr pressure.

In the present invention, the solid phase polymerization can be applied without limitation to resin products utilizing condensation polymerization. For example, the continuous solid-state polymerization apparatus and method of the present invention are aliphatic polyamide polymers and copolymers thereof such as nylon 46, nylon 66, nylon 6, nylon 6,10, nylon 6T, nylon 9T, nylon 10T. , Aromatic polyamide polymers such as nylon 12T and copolymers thereof (high heat resistant nylon resin), copolymers of aromatic polyamides and aliphatic polyamides such as nylon 6T / 66 and nylon 6T / 46/66, polyethylene terephthalate (PET) It may be applied to polyester resins such as resins, polycarbonate (PC) resins, and the like, but is not limited thereto.

In addition, the solid phase polymerization is generally performed using a prepolymer, but for a polymer having a high molecular weight (intrinsic viscosity), in order to have a higher molecular weight to improve heat resistance, the solid phase Polymerization can also be extended.

In the present invention, the prepolymer is a powder having a low apparent specific gravity (e.g., about 0.3 to about 0.5) that can be obtained by rapidly depressurizing (flash process) a conventional prepolymerized solution phase prepolymer under high pressure. Wet cakes having low order polymers of various shapes and sizes (eg, from about 30 μm to about 3 mm), such as chips, particles, etc., containing from about 1 to about 30% by weight of water or organic solvents. It may be in the form, but is not limited thereto. For example, as the prepolymer, the intrinsic viscosity (IV) measured using a Ubbelodhde viscometer at about 25 ° C. after dissolving in a sulfuric acid solution (about 98%) is about 0.09 to about 0.49 dL / g. Phosphorus polymer can be used. Preferably, the intrinsic viscosity of the prepolymer may be about 0.11 to about 0.15 dL / g. In the above range, the prepolymer or the like in the reactor may be attached to reduce or prevent the formation of stagnant sections, and good solid phase polymerization may be performed.

As the feeder 10 used in the present invention, a conventional feeder capable of continuously supplying a prepolymer to a continuous solid-phase polymerization reactor may be used. In the present specification, "feeder" may be used to mean not only a feeder but also a hopper, a chamber, and the like connected thereto. The feeder may be, for example, a loss in weight type quantitative feeder (screw feeder, etc.), a volumetric feeder, or the like, but is not limited thereto.

In an embodiment, the screw feeder may be continuously fed in such a way that the screw rotational speed of the feeder is automatically adjusted to maintain the input target value input to the controller.

The horizontal reactor 20 used in the present invention is a space in which an input part is connected to the feeder 10 and the first connection part to receive a prepolymer from the feeder 10 to perform solid phase polymerization, and the reactor itself has a horizontal axis. Rotation as a reference is characterized in that the stagnation section in which the polymer can be stagnant is removed. A rotary kiln dryer type reactor may be used as the horizontal reactor 20. For example, a flat, hook type, elbow of about 60 to about 120 ° may be formed on the inner wall of the reactor. Rotary kiln-type reactors equipped with flights having various shapes and heights (eg, about 10 to about 800 mm), such as elbows, can be used. The flight allows the polymer at the bottom of the reactor to continuously mix towards the top of the packed bed. The number of flights to be installed may vary depending on the scale of the reactor, but may be about 2 to about 16, preferably about 6 to about 12. For example, in the middle of the inlet of the transverse reactor 20, a flight of about 90 ° elbow can be arranged so that the flight can pull up the polymer as long as possible, and if necessary, the angle of the elbow flight It can be designed by adjusting.

In embodiments, the horizontal reactor 20 may have a diameter (inner diameter) of about 15 to about 240 cm, and may be about 2 to about 20 m in length, but is not limited thereto.

In an embodiment, the transverse reactor 20 can form a slope such that the polymer can flow toward the outlet through gravity flow and reactor rotation. The inclination angle may be, for example, about 0.05 to about 3.0 degrees, preferably about 0.2 to about 1.0 degrees, such that the inlet side of the reactor is located higher than the outlet side.

In addition, the rotational speed (tip speed) of the horizontal reactor 20 may vary depending on the size of the reactor, the required residence time of the polymer used, for example, about 0.03 to about 0.6 m / sec, Preferably about 0.06 to about 0.3 m / sec. Within this range it is possible to reduce or prevent the formation of stagnant sections of the polymer.

In addition, in the horizontal reactor 20, the input rate of the prepolymer may vary depending on the size of the reactor, the required residence time of the polymer used, and may be about 0.1 to about 1,500 kg / hr.

The chamber 30 used in the present invention is a discharge portion of the horizontal reactor 20 is connected through a second connection portion, the polymer in which the solid-phase polymerization is completed in the horizontal reactor 20 is collected, discharged, the conventional solid phase A discharge chamber used in the polymerization reactor can be used. For example, a chamber capable of maintaining a vacuum state by a vacuum pump can be used.

The sealing member 40 used in the present invention leaks gas and liquid from the first and second connections to which the fixed feeder 10 and the chamber 30 and the horizontal reactor 20 which rotate are connected. By preventing the inflow, it is to maintain the feeder 10, the horizontal reactor 20 and the chamber 30 in a vacuum state and to minimize the inflow of air.

In an embodiment, the sealing member 40 may be a magnetic fluid seal. The magnetic fluid seal induces magnetic force formation between a stationary magnet and a rotating part rotating at the center thereof, so that when the magnetic fluid (ferro fluid) is injected, the magnetic fluid is O- between the pole piece and the rotating shaft. It is a device for sealing by forming a film such as a ring. Since the magnetic fluid seal is non-contact, there is almost no friction during rotation. Preferably, a high vacuum seal (magnetic fluid seal) capable of maintaining a degree of vacuum up to about 10 ⁻⁷ torr may be used.

In an embodiment, the maximum allowable vacuum leak of the feeder 10, the lateral reactor 20 and the chamber 30 is determined by the feeder 10, the lateral reactor 20 and the chamber prior to the start of the reaction. When the connection system including (30) is empty and the vacuum is secured by using the vacuum pump to about 1 torr, the pressure is kept about 1 hour while the inlet valve of the vacuum pump is closed. 0.7 torr liter / sec.

2 is a schematic diagram of a continuous solid-state polymerization apparatus according to another embodiment of the present invention. As shown in FIG. 2, in the continuous solid-state polymerization apparatus of the present invention, a vacuum pump 50 may be connected to the chamber 30 or the feeder 10 and the chamber 30.

The vacuum pump 50 used in the present invention maintains the feeder 10, the horizontal reactor 20 and the chamber 30 in a vacuum state, and by-products such as gasified unreacted monomers, oligomers, water vapor, and the like. Can be discharged to the outside. As the vacuum pump 50, a conventional vacuum pump may be used. For example, a dry vacuum pump, a manual vacuum pump, an oil vane type vacuum pump, or the like may be used. In addition, depending on the required degree of vacuum, a vacuum ejector, a vacuum booster, or the like may be connected to the front end of the vacuum pump 50 and used. For example, about one or about two vacuum ejectors, vacuum boosters, etc. may be connected in series, and a vacuum pump 50 may be connected to a rear end thereof.

In embodiments, the steam and the like may be cooled and partial condensation in a compressed state through the vacuum booster, etc., and then introduced and discharged into the final vacuum pump 50. More specifically, the steam and the like is discharged from the horizontal reactor 20, after filtering the solid product discharged together with the vacuum pipe through the cyclone and the like first, the pure water vapor jacketed gas cooler (duplex cooler) After the first cooling through a cooler, such as, the first and second stages of the vacuum booster (booster) is cooled and partially condensed in a compressed state, it may be introduced into the final vacuum pump 50 and discharged. Water vapor discharged to the discharge portion of the vacuum pump 50 may be recovered in its entirety using a condenser, a scrubber, or the like utilizing cooling water.

As shown in FIG. 2, the horizontal reactor 20 may include a pre-heating section, a main heating section, and a cooling section. Each of the sections may be performed in a separate facility, but in the present invention, the preheating, heating, and cooling processes may be performed in one reactor, thereby facilitating maintaining a vacuum state.

In embodiments, the range of each section may vary depending on the polymer used, the reactor size, etc., but the preheating section may range from about one quarter of the total length of the reactor from the input of the transverse reactor 20, The heating section may range from about 2/4 of the total length of the reactor following the preheating section, and the cooling section may be the outlet of the transverse reactor 20 in the range of about 1/4 of the total length of the reactor following the heating section. have.

Each of the above sections may be configured by installing a jacket (temperature control system) such as a jacket through which a heat medium, cooling water, etc. are circulated, an inner coil, and the like, respectively. For example, the preheating section forms a preheating circulator 22 in the preheating section (including the reactor 20 and the feeder 10), which is about 210 ° C. or less, preferably about 150 to about It can be formed by circulating a hot oil of about 210 ℃. In addition, the heating section forms a heating circulator 24 in the heating section, the heating oil of the heating circulator 24 of about 200 to about 300 ℃, preferably about 210 to about 260 ℃ It can be formed by circulating. However, the temperature of the heat medium used in the preheating circulator 22 and the heating circulator 24 may vary depending on the type of polymer to be subjected to the solid state polymerization.

In addition, the cooling section is formed by forming a cooling circulator 26 in the cooling section, spraying at room temperature air through the spray nozzle of the cooling circulator 26, or circulating a refrigerant such as cooling water. Can be. If necessary, a lattice dumping flight may be installed on the inner wall of the reactor 20 in the cooling section so that the polymer to be cooled can be easily advanced toward the discharge portion.

As shown in FIG. 2, the continuous solid-state polymerization apparatus of the present invention is connected to the first hopper 12 to which the prepolymer is introduced from the outside and maintains the atmospheric pressure, and the first hopper 12 is connected to the first at normal pressure. The prepolymer discharged from the hopper 12 is introduced, and about one or more, preferably about two or more

second hoppers

14a, 14b for introducing the prepolymer into the feeder 10 in a vacuum state. It may further include. The

second hoppers

14a and 14b may selectively receive the prepolymers from the first hopper 12 according to the residual amount of the prepolymers, and continuous feeding may be performed when two or more hoppers are alternately operated. For example, the

second hopper

14a, 14b closes the pipe for supplying the prepolymer to the feeder 10, opens an upper vent to change the internal pressure from vacuum to atmospheric pressure, or the first The pipe receiving the prepolymer from the hopper 12 may be closed, and the gas may be discharged to the vacuum pump 50 to change the internal pressure from normal pressure to vacuum. Thus, when using two or more

second hoppers

14a and 14b, one of the

second hoppers

14a or 14b feeds the prepolymer to the feeder 10 in a vacuum and the other second The

hopper

14a or 14b receives the prepolymer from the first hopper 12 at atmospheric pressure, and when there is almost no residual amount of prepolymer in the one

second hopper

14a or 14b, it is immediately replaced and vacuumed. In the feeder 10 can be prepared (stand-by) to supply the prepolymer. By repeating this process, the precopolymer can be continuously added without affecting the vacuum state of the horizontal reactor 20.

In addition, the continuous solid-state polymerization apparatus, the polymer is a solid-phase polymerized polymer discharged from the chamber 30 is discharged from the chamber 30 is connected to the chamber 30, the agent for discharging the polymer to the outside at atmospheric pressure It may further include three hoppers (32a, 32b). The

third hoppers

32a and 32b may change the internal pressure to a vacuum state or a normal pressure in the same manner as the

second hoppers

14a and 14b, and may be in a vacuum state from the chamber 30 to maintain the vacuum state. After the transfer of the polymer in which the solid state polymerization is completed, the connection with the chamber 30 may be blocked to change the atmospheric pressure and discharge the polymer to the outside without affecting the vacuum state of the reactor.

In an embodiment, the polymer having completed the solid phase polymerization may have an intrinsic viscosity (IV) of about 0.5 to about 1.5 dL / g, but is not limited thereto.

Continuous solid phase polymerization method according to the present invention is a solid phase polymerization method using the continuous solid phase polymerization apparatus, the step of introducing a prepolymer into the feeder (10); Solid-phase polymerization of the prepolymer introduced in the horizontal reactor (20); And discharging the solid phase polymerized polymer into the chamber 30, wherein the steps are performed continuously.

Here, the prepolymer may be introduced into the feeder 10 through the first and

second hoppers

12, 14a, and 14b, and the polymer having completed the solid phase polymerization may be added to the third hopper ( 32a, 32b) may be discharged to the outside.

In addition, the solid phase polymerization may be performed through a preheating section, a heating section, and a cooling section of the horizontal reactor 20.

In embodiments, the solid phase polymerization may be carried out under a pressure of about 0.1 to about 100 torr, preferably about 3 to about 50 torr. In the above range, the whiteness of the polymerized polymer product without the inert gas may be excellent.

Since the solid phase polymerization method is continuously performed in a vacuum state without the use of an inert gas, it is possible to save the cost of recovery and recycling of the inert gas, and to prevent deterioration of quality due to the active gas.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

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

실시예Example

실시예 1Example 1

As a horizontal reactor 20 of Figs. 1 and 2, a cylindrical horizontal rotary kiln reactor having an inner diameter of 600 mm and an axial length of 7,000 mm was used, and a slope of 0.2 ° such that the outlet side was lowered compared to the inlet. Wet cake with a mixed apparent specific gravity of 0.33, wherein the low dimensional polymer of the particulate polyamide resin having an average particle size of 0.7 mm and an intrinsic viscosity (IV) of 0.2 dL / g comprises 5% by weight of water as a prepolymer. (wet cake) was used. The prepolymer was used as a feeder 10, using a screw feeder in which a hot oil of 80 ° C. was circulated through a jacket (not shown) installed on the outer wall of the

feeder

10, and 10 kg / The lateral reactor 20 was fed continuously at a constant rate of hr. The reactor 20 was circulated at a constant temperature of 170 ° C. through a preheating jacket 22 installed on the outer wall of the reactor 20 to form a preheating section (length: 1,500 mm), and the heating jacket 24 The heat medium at 245 ° C. was circulated to form a heating section (length: 4,000 mm). The polymer was allowed to have an average residence time of 4.5 to 5.0 hours in the preheating section and the heating section, and then continuously moved to the cooling section (length: 1,500 mm) formed by the cooling jacket 26. At this time, the pressure inside the reactor was maintained in a vacuum condition through a vacuum pump system 50 installed with a vacuum booster (vacuum booster) in front of the manual vacuum pump to maintain a vacuum of 5 torr level. In addition, the cooling section is installed in the cooling jacket 26 including a hollow circular air supply chamber (chamber) in a space spaced apart from the outer wall of the reactor 20 by the chamber at room temperature air introduced from the outside Through the method of spraying to the outer wall surface of the reactor 20 through the reactor outer wall and the polymer inside to cool. In addition, the rotation speed (tip speed) of the reactor 20 was 0.19 m / sec (6 RPM).

실시예 2Example 2

As a horizontal reactor 20 of Figs. 1 and 2, a cylindrical horizontal rotary kiln reactor having an inner diameter of 600 mm and an axial length of 7,000 mm was used, and a slope of 0.2 ° such that the outlet side was lowered compared to the inlet. As a prepolymer, a low dimensional polymer of polycarbonate resin having an intrinsic viscosity (IV) of 0.23 dL / g was dissolved in chloroform at a certain concentration, and a powder having an average particle diameter of 1.0 mm that was crystallized using a mixed solvent of acetone / methanol was used. . The prepolymer is used as a feeder 10, and a constant temperature of 10 kg / hr is used by using a screw feeder in which a hot oil of 80 ° C. is circulated through a jacket (not shown) installed on the outer wall of the feeder. The transverse reactor 20 was fed continuously at a rate. The reactor 20 was circulated at a constant temperature of 200 ° C. through the preheating jacket 22 installed on the outer wall of the reactor 20 to form a preheating section (length: 1,500 mm), and the heating jacket 24 The heat medium at 240 ° C. was circulated to form a heating section (length: 4,000 mm). The polymer was allowed to have an average residence time of 4.5 to 5.0 hours in the preheating section and the heating section, and then continuously moved to the cooling section (length: 1,500 mm) formed by the cooling jacket 26. At this time, the pressure inside the reactor was maintained in a vacuum condition through a vacuum pump system 50 installed with a vacuum booster (vacuum booster) in front of the manual vacuum pump to maintain a vacuum of 5 torr level. In addition, the cooling section is installed in the cooling jacket 26 including a hollow circular air supply chamber (chamber) in a space spaced apart from the outer wall of the reactor 20 by the chamber at room temperature air introduced from the outside Through the method of spraying to the outer wall surface of the reactor 20 through the reactor outer wall and the polymer inside to cool. In addition, the rotation speed (tip speed) of the reactor 20 was 0.19 m / sec (6 RPM).

실시예 3Example 3

As a horizontal reactor 20 of Figs. 1 and 2, a cylindrical horizontal rotary kiln reactor having an inner diameter of 600 mm and an axial length of 7,000 mm was used, and a slope of 0.2 ° such that the outlet side was lowered compared to the inlet. As the prepolymer, a low dimensional polymer of particulate polyethylene terephthalate resin having an average particle size of 2 mm and an intrinsic viscosity (IV) of 0.30 dL / g was used. The prepolymer is used as a feeder 10, and a constant temperature of 10 kg / hr is used by using a screw feeder in which a hot oil of 80 ° C. is circulated through a jacket (not shown) installed on the outer wall of the feeder. The transverse reactor 20 was fed continuously at a rate. The reactor 20 was circulated at a constant temperature of 220 ° C. through a preheating jacket 22 installed on the outer wall of the reactor 20 to form a preheating section (length: 1,500 mm), and a heating jacket 24 The heating medium (length: 4,000 mm) was formed by circulating the heat medium at 260 ° C.). The polymer was allowed to have an average residence time of 4.5 to 5.0 hours in the preheating section and the heating section, and then continuously moved to the cooling section (length: 1,500 mm) formed by the cooling jacket 26. At this time, the pressure inside the reactor was maintained in a vacuum condition through a vacuum pump system 50 installed with a vacuum booster (vacuum booster) in front of the manual vacuum pump to maintain a vacuum of 5 torr level. In addition, the cooling section is installed in the cooling jacket 26 including a hollow circular air supply chamber (chamber) in a space spaced apart from the outer wall of the reactor 20 by the chamber at room temperature air introduced from the outside Through the method of spraying to the outer wall surface of the reactor 20 through the reactor outer wall and the polymer inside to cool. In addition, the rotation speed (tip speed) of the reactor 20 was 0.19 m / sec (6 RPM).

실험예Experimental Example

The intrinsic viscosity, color and whiteness of the polyamide having completed the solid phase polymerization were measured, and after the reaction, the polymer adhesion of the inner wall of the reactor was confirmed and shown in Table 1 below.

Property evaluation method

(1) Confirmation of adhesion: After blowing with air of 3 kg / cm ² G pressure on the surface of the reactor was confirmed the surface state visually.

◎: Almost no adhesion (Small amount is attached before air blowing but can be removed by air)

○: Small amount of attachment after air blowing but can be easily removed by hand

△: It is attached after blowing by air and can be easily removed by applying physical force with the instrument.

×: It is attached after blowing by air, and it is not easily removed even if physical force is applied by the instrument.

(2) Intrinsic Viscosity (IV) Determination: After dissolving in sulfuric acid solution (98%), it was measured using a Ubbelodhde viscometer at 25 ° C.

(3) Color and Whiteness Measurements: Three samples each were taken and placed in a solid sample sample holder and 5 colors (SCI) per sample (whiteness (L) and yellow) using a CM-2600d Spectrophtometer from KONICA MINOLTA. The yellowness (b *)) was measured 15 times in total and the average value was calculated.

(4) Number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (PDI) measurement: Measured using GPC (Gel Permeation Chromatography).

Table 1

	Example 1	Example 2	Example 3
Intrinsic Viscosity (dL / g)	0.98	0.93	0.89
Mn (g / mol)	9.6k	12.1k	11.1k
Mw (g / mol)	32.6k	27.9k	23.3k
PDI	3.4	2.3	2.1
Whiteness (L)	90	92	93
Yellowness (b *)	6.72	5.42	4.71
Adhesion	○	○	○

From the results of Table 1, when the polymer is solid-phase polymerized using the continuous solid-state polymerization apparatus of the present invention, the polymer having a commercially significant intrinsic viscosity of 0.8 to 1.2 dL / g without inert gas, white and yellow It can be seen that it can be produced economically without deterioration.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

A feeder for continuously feeding the prepolymer;

A horizontal reactor connected to the feeder through a first connection part to receive a prepolymer from the feeder to perform solid phase polymerization, and to rotate the reactor itself; And

A chamber connected to the horizontal reactor via a second connection to receive and discharge the polymer that has undergone solid phase polymerization discharged from the horizontal reactor,

And the feeder, the horizontal reactor, and the chamber are in a vacuum state.
The continuous solid state polymerization apparatus according to claim 1, wherein the continuous solid state polymerization apparatus includes a sealing member for preventing leakage of gas and liquid from the first connection portion and the second connection portion.
The continuous solid-state polymerization apparatus according to claim 2, wherein the sealing member is a magnetic fluid seal.
The continuous solid-state polymerization apparatus according to claim 1, wherein a vacuum pump is connected to the chamber.
The continuous solid-state polymerization apparatus according to claim 1, wherein a vacuum pump is further connected to the feeder.
The continuous solid-state polymerization apparatus according to claim 1, wherein the horizontal reactor includes a preheating section, a heating section, and a cooling section.
According to claim 1, The continuous solid-state polymerization device,

A first hopper to which the prepolymer is introduced from the outside and maintains atmospheric pressure; And

And a second hopper connected to the first hopper to discharge the prepolymer discharged from the first hopper at atmospheric pressure and to introduce the prepolymer into the feeder in a vacuum state. .
The continuous solid-state polymerization apparatus of claim 1, further comprising a third hopper connected to the chamber to discharge the polymer from the chamber in a vacuum state, and discharge the polymer to the outside at atmospheric pressure. Continuous solid-state polymerization apparatus, characterized in that.
The continuous solid-state polymerization apparatus according to claim 1, wherein the prepolymer is a polymer having an intrinsic viscosity (IV) of about 0.09 to about 0.49 dL / g.
The continuous solid-state polymerization apparatus according to claim 1, wherein the polymer in which the solid phase polymerization is completed has an intrinsic viscosity (IV) of about 0.5 to about 1.5 dL / g.
A solid state polymerization method using the continuous solid state polymerization device according to any one of claims 1 to 10,

Injecting a prepolymer into the feeder;

Solid-phase polymerization of the prepolymer introduced in the horizontal reactor; And

Discharging the solid phase polymerized polymer into the chamber,

Continuous solid phase polymerization method, characterized in that the steps are carried out continuously.
12. The process of claim 11 wherein the solid phase polymerization is carried out under a pressure of about 0.1 to about 100 torr.