KR100888882B1 - Process for producing poly trimethylene terephthalate - Google Patents

Abstract

A process for producing poly (trimethylene terephthalate) is provided to mass-produce the poly (trimethylene terephthalate) by using one or two reactors simply and conveniently. A process for producing poly (trimethylene terephthalate) comprises a step of feeding 1,3- propanediol and terephthalic acid or 1,3- propanediol and dimethylterephthalate, to an input hole(F11) of one or two reactors or one kneader-type extruder, so that the molar ratio of propylene and terephthalate group becomes 1.1-2.2; a step of producing the low-molecular-weight poly (trimethylene terephthalate) through direct esterification or transesterification within a reactor or kneader-type extruder; a step of producing the high molecular weight poly (trimethylene terephthalate) through polycondensation by feeding a polymerization catalyst and additive in a secondary input hole(F12) of a reactor or kneader-type extruder and applying the vacuum at the later part(P2) of the reactor or kneader type extruder; and a step of palletizing it by using pelletizer connected to the reactor or kneader type extruder.

Description

Process for producing poly trimethylene terephthalate

The present invention is a method for preparing 'poly (trimethylene terephthalate)', also commonly referred to as 'poly (1,3-propylene terephthalate)'. It is about. In the present invention, a method for preparing poly (trimethylene terephthalate), which simplifies the manufacturing process of poly (trimethylene terephthalate) so as to prepare poly (trimethylene terephthalate) using one or two reactors. To present.

Poly trimethylene terephthalate (hereinafter referred to as 'PTT') is a kind of polyester yarn made by changing the existing synthetic structure to make the texture the same as or better than nylon, and refers to a skin-like yarn. Such poly (trimethylene terephthalate) manufacturing process is 1,3-propanediol and terephthalic acid or 1,3-propanediol and dimethyl terephthalate ( Low molecular weight poly (trimethylene terephthalate) through mixing of di-methyl terephthalate raw materials, direct esterification of 1,3-propanediol and terephthalic acid, or transesterification of 1,3-propanediol and dimethyl terephthalate Solid phase polymerization after crystallization of high molecular weight poly (trimethylene terephthalate), step of producing high molecular weight poly (trimethylene terephthalate) through polycondensation process using a transesterification reaction from low molecular weight polyester At least three or four stages of the manufacturing process, such as stages, are used. It is common to use a reactor.

A batch production process of poly (trimethylene terephthalate) is disclosed in US Pat. No. 5,340,909. U.S. Patent No. 5,340,909 discloses poly (trimethylene terephthalate) by performing a transesterification reaction using a lower dialkyl terephthalate ester as starting material or a direct condensation reaction of terephthalic acid followed by a batch using an autoclave. Disclosed is a method of manufacturing.

A continuous process for producing poly (trimethylene terephthalate) is introduced in Korean Patent Registration No. 10-0713759 and Patent Registration No. 10-0713761 of DuPont. Here, a low molecular weight polyester is produced by transesterification from dimethyl terephthalate and 1,3-propanediol or by direct esterification of terephthalic acid and 1,3-propanediol, which are continuously transferred to a prepolymerization reactor. Preparing a poly (trimethylene terephthalate) prepolymer having a relative viscosity of about 5 or more, and continuously supplying it back to the final polymerization reactor to prepare a high molecular weight poly (trimethylene terephthalate) having a relative viscosity of about 17 or more. It introduces a poly (trimethylene terephthalate) continuous manufacturing method comprising a. Here, a large number of reactors (at least three or more) are used by making different types of reactors for each stage of manufacture.

It would be highly desirable to provide a new process for the production of poly (trimethylene terephthalate), ie a process that reduces the number of reactors used.

The present invention provides a method for producing poly (trimethylene terephthalate) which simplifies the manufacturing process of poly to produce poly (trimethylene terephthalate) (PTT) using one or two reactors. For the purpose of

The present invention presents a simplified process for producing poly (trimethylene terephthalate) (PTT) using an extruder reactor. Specifically, unlike the manufacturing process of the poly (trimethylene terephthalate) using the three to four reactors known in the prior art to produce a poly (trimethylene terephthalate) in one or two extruder-type reactor present.

More specifically, one or two extruder screws are mounted inside the reactor, and the reactor is divided into two parts of the first half and the second half by the separation controller S, and the raw material inlet F11 in the first half P1 of the reactor. ) And outlet (V11) for discharging water or methanol, and at least one auxiliary inlet (F12) for injecting catalyst and additives in the second half of the reactor (P2) and at least one connection (V12) connected to the vacuum pump. By using the reactor configured, i) 1,3-propanediol and terephthalic acid or 1,3-propanediol and dimethyl terephthalate, the raw material of the first half of the extruded reactor P1 such that the molar ratio of propylene to terephthalate groups is 1.1 to 2.2. Feed to the inlet, and ii) produce low molecular weight poly (trimethylene terephthalate) by direct esterification or transesterification in the first half of the extruder reactor (P1). Iii) high molecular weight poly (trimethylene terephthalate) by polycondensation reaction while supplying the polymerization catalyst and the additive to the auxiliary inlet port F12 of the latter part P2 of the extruder type reactor and applying a vacuum to the second part P2 of the reactor. ) And iv) a series of steps of pelletizing using a pelletizer directly connected to an extruder reactor to prepare poly (trimethylene terephthalate).

Alternatively, two extruder reactors (R1, R2) are connected in series, the first reactor (R1) is equipped with a raw material inlet (F21) and the outlet (V21) for water or methanol discharge, the second The reactor (R2) is equipped with one or more auxiliary inlets (F22) for the addition of the polycondensation catalyst and additives, and the reactor connected to the two extruder-type reactors equipped with one or more connections (V22) connected to the vacuum pump in series To obtain a poly (trimethylene terephthalate) by supplying a raw material, producing a low molecular weight poly (trimethylene terephthalate), generating a high molecular weight poly (trimethylene terephthalate), and pelletizing Manufacture.

In addition, a kneader extruder equipped with a raw material inlet (K-F1) and an outlet (K-V1), the outlet (K-V1) is a kneader configured to be connected to an external or vacuum pump through a control valve Using a (Kneader) type extruder, feeding the raw materials, producing low molecular weight poly (trimethylene terephthalate), forming high molecular weight poly (trimethylene terephthalate), and pelletizing To produce poly (trimethylene terephthalate).

In the present invention, the use of one or two reactors can provide a simplified and convenient process for producing poly (trimethylene terephthalate) (PTT).

Figure 1 schematically shows the shape of the extruder reactor. Injecting 1,3-propanediol and terephthalic acid into the first feed inlet (F11) of the extruder reactor, wherein the molar ratio of 1,3-propanediol to terephthalic acid introduced is maintained to 1.1 to 2.2, preferably 1.4 to 1.6 do. The raw materials are mixed in the outside and then put into the first raw material inlet (F11) of the extruder-type reactor, or each raw material is put into the raw material inlet (F11) to allow the reaction to proceed simultaneously with mixing. At this time, the catalyst may be added at the same time as the raw material, or may not be added. If a catalyst is added, a direct esterification catalyst may be added for direct esterification of 1,3-propanediol and terephthalic acid in the first half of the reactor (P1). The direct esterification catalyst used at this time is an organo-titanium and an organo-tin compound, each added in an amount sufficient to produce at least 20 ppm titanium or at least 50 ppm tin based on the weight of the final polymer. The input material is low molecular weight poly (trimethylene terephthalate) through direct esterification of 1,3-propanediol and terephthalic acid in the first half of the extruder reactor (P1) up to the auxiliary inlet (F12) located in the middle of the reactor. Becomes At this time, the temperature of the first half (P1) of the extruder reactor is maintained at 180 ~ 240 ℃, preferably 200 ~ 210 ℃. In addition, in the first part (P1) of the extruder-type reactor, the outlet (V11) is configured to prevent water from being reversed due to moisture so that water generated through direct esterification of 1,3-propanediol and terephthalic acid can be removed well. do.

The reactant produced in the first half of the reactor P1, that is, the low molecular weight poly (trimethylene terephthalate), is separated by the separation controller S disposed between the first half P1 and the second half P2 of the extruder reactor. The amount passed to P2) is controlled. After the raw material is introduced through the raw material inlet (F11) of the first half of the extruder reactor, direct esterification of 1,3-propanediol and terephthalic acid proceeds to generate low molecular weight poly (trimethylene terephthalate). The viscosity of is increased. Viscosity is determined according to the reaction degree of the raw material, and the viscosity of the reactant is measured in the first half (P1) by measuring the torque value applied to the screw, and when the viscosity is increased to a certain level, opening and closing of the separation control device (S) The apparatus is operated to move the reactants to the latter part P2 of the extruded reactor. At this time, it is preferable to operate the opening and closing device of the separation control device (S) at the viscosity when the conversion rate of the raw material introduced into the first half (P1) of the reactor is 70% or more and less than 95%, preferably 70% or more and less than 80%. When the conversion rate of the input raw material is less than 70%, the transesterification reaction in the second half of the reactor (P2) is delayed, so that it is difficult to obtain a high molecular weight polymer. When the conversion rate is 95% or more, the residence time in the first half of the reactor (P1) is too long. It has a disadvantage that it is not efficient in terms of economic efficiency due to the long response time. The function of this separation control device (S) can be obtained by using a series of two extruder-type reactors without a separation control device as shown in Figure 2 by using a series.

As described above, the low molecular weight poly (trimethylene terephthalate) transferred from the first half (P2) to the second half (P2) of the reactor by the separation controller (S) reaches the secondary inlet (F12) and polycondensates together with the transesterification catalyst. Upon entering the reaction, high molecular weight poly (trimethylene terephthalate) is produced in the latter part P2 of the reactor-type extruder. At this time, useful catalysts for the transesterification process may include organic and inorganic compounds of titanium, lanthanum and zinc. The titanium catalyst is preferably, for example, tetraisopropyl titanate and tepraisobutyl titanate, and is added in an amount sufficient to produce 20 to 90 ppm (million parts) of titanium based on the weight of the polymer. Another useful catalyst is lanthanum acetate, which may be added in an amount sufficient to produce 100 to 250 ppm (parts per million) of lanthanum by weight of the polymer. Following transesterification, lanthanum is inactivated by adding phosphoric acid in an amount sufficient to produce 10 to 50 weight ppm of phosphorus based on the final polymer. Tetraisopropyl titanate or tetraisobutyl titanate is then added as a polycondensation catalyst in an amount sufficient to produce 10 to 50 ppm titanium based on the weight of the polymer. The amount of other transesterification catalyst is adjusted to produce the same effect as 20 to 90 ppm titanium. As the stabilizer added together with the catalyst, a phosphate-based or aminoalkyl-based compound is suitable. More specifically, neopentyl (diaryl) oxytri (dioctyl) phosphato titanate and neopentyl (diaryl) oxy Group consisting of tri (dioctyl) pyrophosphato titanate, neopentyl (diaryl) oxytri (N-ethylenediamino) ethyl titanate and neopentyl (diaryl) oxytri (m-amino) phenyl titanate The amount is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of terephthalic acid as a raw material. If the amount of the stabilizer is less than 0.01 part by weight, the effect as a stabilizer is insufficient, and the polymer is thermally decomposed, thereby significantly reducing the physical properties. If the amount is more than 0.5 part by weight, the color of the polymer is deteriorated and the strength is decreased. There are disadvantages such as being. Other additives may also be used as color additives such as phosphoric acid, matting agents such as titanium dioxide, and other dyeable modifiers, pigments and bleaches as additives to enhance the function of the final polymer. The transesterification catalyst as described above may be introduced into the auxiliary inlet (F12) of the latter part (P2) immediately before the transesterification reaction, that is, the polycondensation reaction, but before the direct esterification reaction, that is, the raw material and At the same time, it may be introduced into the raw material inlet (F11) of the first half (P1) of the reactor. In this case, since the catalyst has already been introduced into the first half P1, it is not necessary to reintroduce the catalyst into the auxiliary inlet F12 of the second half P2 before the polycondensation reaction occurs.

In the latter part (P2) of the extruder reactor, the low molecular weight poly (trimethylene terephthalate) from the first part (P1) is mixed with the catalyst added at the auxiliary inlet (F12), and the high molecular weight poly (trimethylene terephthalate) Will be generated. This is achieved by heating, mixing, vacuum and catalyst of the reactor in the latter part P2 of the reactor. In the latter part P2 of the reactor, it is desirable to maximize the molecular weight of the final polymer so that it can be used directly in fiber spinning or other plastic molding processes. The temperature of the latter part P2 of the reactor is maintained at about 200 to 260 ° C, preferably about 220 to 240 ° C. Extruder type reactor used in the present invention has one or two screws inside the reactor to improve the mixing of the polymer to improve the transesterification reaction efficiency, the frictional heat received by the polymer compared to the conventional polymerization reactor system By reducing the thermal degradation of the local polymer, the yellowness of the final polymer can be reduced. In addition, since the reactor is configured in the form of a general extruder, it is possible to precisely control the temperature inside the reactor by dividing the second half of the reactor (P2) into several parts to prevent the thermal decomposition due to the local temperature rise inside the reactor. There is this. In the latter part (P2) of the extruder reactor, it is desirable to remove 1,3-propanediol produced by the transesterification reaction to the outside in order to increase the molecular weight of the polymer, which is connected to an external vacuum pump to apply a vacuum. The connection part V12 is comprised, and it is preferable to maintain the pressure of the latter half part P2 of about 0.5-3.0 mmHg. Maintaining the pressure of the second half (P2) of the extruder reactor at about 0.5 to 3.0 mmHg, the 1,3-propanediol produced by the transesterification reaction is removed to the outside through the connection (V12) connected to the vacuum pump, When the boiling point of 1.3-propanediol is vacuumed to 200 ^° C. in the reactor, high molecular weight polymer remains in the reactor and only 1,3-propanediol is removed to the outside to decompose the polymer by 1,3-propanediol. The reaction is prevented and the transesterification reaction continues to increase the molecular weight of the polymer. At this time, 1,3-propanediol removed to the outside of the reactor may be recovered through a condenser and used as a raw material again.

The final polymer produced through the second half of the reactor (P2) is passed to a polymer outlet configured at the end of the reactor (P2) underwater die-face pelletizing system connected directly to the die of the second half of the reactor (P2). The final polymer, which is manufactured in pellet form and transported with the coolant, is packaged through dehydration and drying process by a device that manufactures pellets in the form of pellets. Can be obtained. In this case, the pelletizer used is a water-cooled underwater die-face pelletizer used in an extruder of a general polymer resin, and if necessary, an additional device for crystallization of the polymer during dehydration and drying may be added.

Poly (trimethylene terephthalate), the final polymer prepared in this manner, was determined by intrinsic viscosity measurement in 60/40 wt% phenol / 1,1,2,2-tetrachloroethane according to ASTM D 4603-96. Poly (trimethylene terephthalate) having a relative viscosity of about 0.5 dl / g or more.

2 shows an embodiment in the form of two extruder reactors connected in series. Process conditions, such as the temperature and pressure of each reactor, that is, the first reactor (R1) and the second reactor (R2) shown in Figure 2 is the first half (P1) and second half (P2) of the extruder reactor described in FIG. The polymer is prepared under the same process conditions, and the content of raw materials, catalysts, and additives used is the same as that of the extruder reactor of FIG. 1. In addition, the transesterification catalyst may be introduced into the second reactor (R2) immediately before the transesterification reaction, that is, the polycondensation reaction, but the first reactor (R1) at the same time as the direct esterification reaction, i.e. You can also put in. In this case, since the catalyst has already been added, it is not necessary to add the catalyst again to the second reactor (R2) before the polycondensation reaction occurs.

In addition, as shown in Figure 3, it is also possible to produce the desired poly (trimethylene terephthalate) by operating a batch-type extruder reactor without a separate control device (S) in a batch (type). When extruder type reactors are operated in batch-type, such extruder type reactors are sometimes referred to as kneader type extruders or kneader type reactors. In the case of a batch operation, each reaction step proceeds sequentially to one kneader type reactor. Referring to the kneader reactor shown in FIG. 3, 1,3-propanediol and terephthalic acid are introduced into the raw material inlet (K-F1) of the kneader reactor, wherein the molar ratio of 1,3-propanediol to terephthalic acid is 1.1. To 2.2, preferably 1.4 to 1.6. The raw materials are mixed externally and then put into the raw material inlet (K-F1), or each raw material is put into the raw material inlet (K-F1) to allow the reaction to proceed simultaneously with mixing. The raw material introduced in this way produces low molecular weight poly (trimethylene terephthalate) through the direct esterification of 1,3-propanediol and terephthalic acid. At this time, the temperature of the kneader reactor is maintained at 180 ~ 240 ℃, preferably 200 ~ 210 ℃. In addition, the outlet port (K-V1) is configured to remove water generated through the direct esterification reaction of 1,3-propanediol and terephthalic acid in the lower kneader reactor, thereby preventing the reverse reaction caused by water. At this time, by using the control valve of the outlet (K-V1) to block the connection between the kneader-type extruder and the vacuum pump and to adjust the moisture (vent) to the outside (Vent). As the direct esterification progresses, low molecular weight poly (trimethylene terephthalate) is produced, and when the conversion rate of the raw material into which the viscosity is introduced into the reactor reaches 70% or more and less than 95%, the transesterification catalyst is added to the raw material inlet. And an additive is added to carry out the polycondensation reaction of the low molecular weight poly (trimethylene terephthalate). (The catalyst and the additive may be added simultaneously with the addition of the raw material. There is no need to re-inject before the reaction. Operation conditions under which the polycondensation reaction proceeds are performed in the same manner as the operation conditions of the second half of the extruder type reactor P2 of FIG. 1. The final polymer produced through the kneader extruder is pelletized using a water cooled pelletizer directly connected to the die of the extruder, and then the final product is manufactured by dehydration and drying.

In addition to the above-described raw materials for the production of poly (trimethylene terephthalate) can be prepared using 1,3-propanediol and dimethyl terephthalate raw materials, the production method is as follows. 1,3-propanediol and dimethyl terephthalate are added together with the transesterification catalyst to the first feed inlet (F11) of the extruder reactor of Figure 1, wherein the molar ratio of 1,3-propanediol to dimethyl terephthalate Maintain 1.1 to 2.2, preferably 1.4 to 1.6. The raw materials are mixed in the outside and then put into the first raw material inlet (F11) of the extruder-type reactor, or each raw material is put into the raw material inlet (F11) to allow the reaction to proceed simultaneously with mixing. The raw material thus introduced is low molecular weight poly (trimethylene terephthalate) through transesterification of 1,3-propanediol and dimethyl terephthalate in the first half of the extruder reactor (P1) up to the auxiliary inlet (F12) located in the middle of the reactor. ) At this time, the temperature of the first half (P1) of the extruder reactor is maintained at 180 ~ 240 ℃, preferably 200 ~ 210 ℃. In addition, in the first part (P1) of the extruder type reactor, the outlet (V11) is configured so that methanol generated through the transesterification reaction of 1,3-propanediol and dimethyl terephthalate can be well removed. prevent.

The reactant produced in the first half of the reactor P1, that is, the low molecular weight poly (trimethylene terephthalate), is separated by the separation controller S disposed between the first half P1 and the second half P2 of the extruder reactor. The amount passed to P2) is controlled. After the raw material is introduced through the raw material inlet (F11) of the first part of the extruder reactor (P1), the transesterification reaction of 1,3-propanediol and dimethyl terephthalate proceeds to generate a low molecular weight poly (trimethylene terephthalate) reactor. The internal viscosity will increase. Viscosity is determined according to the reaction degree of the raw material, and the viscosity of the reactant is measured in the first half (P1) by measuring the torque value applied to the screw, and when the viscosity is increased to a certain level, opening and closing of the separation control device (S) The apparatus is operated to move the reactants to the latter part P2 of the extruded reactor. At this time, it is preferable to operate the opening and closing device of the separation control device (S) at the viscosity when the conversion rate of the raw material introduced into the first half (P1) of the reactor is 70% or more and less than 95%, preferably 70% or more and less than 80%. When the conversion rate of the input raw material is less than 70%, the transesterification reaction in the second half of the reactor (P2) is delayed, so that it is difficult to obtain a high molecular weight polymer. When the conversion rate is 90% or more, the residence time in the first half of the reactor (P1) is too long. It has a disadvantage that it is not efficient in terms of economic efficiency due to the long response time. The function of such a separation control device (S) can be obtained by connecting the two extruder-type reactors without a separation control device in series as shown in FIG.

As described above, the low molecular weight poly (trimethylene terephthalate) transferred from the first half (P2) to the second half (P2) of the reactor by the separation controller (S) reaches the secondary inlet (F12) and polycondensates together with the transesterification catalyst. Upon entering the reaction, high molecular weight poly (trimethylene terephthalate) is produced in the latter part P2 of the extruder reactor. The transesterification catalyst may be further added to the auxiliary inlet (F12) of the second half of the reactor (P2). The auxiliary inlet (F12) is added to the stabilizer mentioned above to prevent the polymer from thermally deteriorated to significantly reduce the physical properties, and other additives, such as color inhibitors, quenchers, dyeing modifiers, pigments and bleaches to function of the final polymer Can improve. In the second half part P2 of the extruder type reactor, the low molecular weight poly (trimethylene terephthalate), which has been passed from the first part P1, is produced through high-molecular weight poly (trimethylene terephthalate) through transesterification. This is achieved by heating, mixing, vacuum and catalyst of the reactor in the latter part P2 of the reactor. In the latter part P2 of the reactor, it is desirable to maximize the molecular weight of the final polymer so that it can be used directly in fiber spinning or other plastic molding processes. The temperature of the latter part P2 of the reactor is maintained at about 200 to 260 ° C, preferably about 220 to 240 ° C. Extruder type reactor used in the present invention has one or two screws inside the reactor to improve the mixing of the polymer to improve the transesterification reaction efficiency, the friction heat received by the polymer compared to the conventional polymerization reactor system This reduces the yellowness of the final polymer by preventing thermal decomposition of the localized polymer. In addition, since the reactor is configured in the form of a general extruder, it is possible to precisely control the temperature inside the reactor by dividing the second half of the reactor (P2) into several parts to prevent the thermal decomposition due to the local temperature rise inside the reactor. There is this. In the latter part (P2) of the extruder reactor, it is desirable to remove 1,3-propanediol produced by the transesterification reaction to the outside in order to increase the molecular weight of the polymer, which is connected to an external vacuum pump to apply a vacuum. The connection part V12 is comprised, and it is preferable to maintain the pressure of the latter half part P2 of about 0.5-3.0 mmHg. Maintaining the pressure of the second half (P2) of the extruder reactor at about 0.5 to 3.0 mmHg, the 1,3-propanediol produced by the transesterification reaction is removed to the outside through the connection (V12) connected to the vacuum pump, This means that when the boiling point of 1.3-propanediol is vacuumed to 200 ^o C, the polymer remains in the reactor and only 1,3-propanediol is removed to prevent decomposition of the polymer by 1,3-propanediol. The transesterification reaction continues to increase the molecular weight of the polymer. At this time, 1,3-propanediol removed to the outside of the reactor may be recovered through a condenser and used as a raw material again.

The final polymer produced through the second half of the reactor (P2) is passed to a polymer outlet configured at the end of the reactor (P2) underwater die-face pelletizing system connected directly to the die of the second half of the reactor (P2). The final polymer, which is manufactured in pellet form and conveyed with the coolant, is packaged through dehydration and drying process by a device that manufactures pellets in the form of pellets. Can be obtained. In this case, the pelletizer used is a water-cooled underwater die-face pelletizer used in an extruder of a general polymer resin, and if necessary, an additional device for crystallization of the polymer during dehydration and drying may be added.

Poly (trimethylene terephthalate), the final polymer prepared in this manner, was determined by intrinsic viscosity measurement in 60/40 wt% phenol / 1,1,2,2-tetrachloroethane according to ASTM D 4603-96. Poly (trimethylene terephthalate) having a relative viscosity of about 0.5 dl / g or more.

The production of poly (trimethylene terephthalate) using 1,3-propanediol and dimethyl terephthalate as a raw material can be prepared by connecting two extruder reactors in series as shown in FIG. Process conditions, such as the temperature and pressure of each reactor, that is, the first reactor (R1) and the second reactor (R2) shown in Figure 2 is the first half (P1) and second half (P2) of the extruder reactor described in FIG. The polymer is prepared under the same process conditions, and the content of raw materials, catalysts, and additives used is the same as that of the extruder reactor of FIG. 1.

In addition, as shown in Figure 3, by operating a single extruder-type reactor without a separation control device (S) in a batch (batch-type) by using the 1,3-propanediol and dimethyl terephthalate raw material desired poly ( Trimethylene terephthalate) may be prepared. Referring to the kneader type reactor shown in FIG. 3, 1,3-propanediol and dimethyl terephthalate are introduced into the raw material inlet (K-F1) of the kneader type reactor, wherein 1,3-propanediol to dimethyl terephthalate are added. The molar ratio of is maintained at 1.1 to 2.2, preferably 1.4 to 1.6. The raw materials are mixed externally and then put into the raw material inlet (K-F1), or each raw material is put into the raw material inlet (K-F1) to allow the reaction to proceed simultaneously with mixing. The input raw material is a low molecular weight poly (trimethylene terephthalate) is produced through the transesterification reaction of 1,3-propanediol and dimethyl terephthalate. At this time, the temperature of the kneader reactor is maintained at 180 ~ 240 ℃, preferably 200 ~ 210 ℃. In addition, the outlet port (K-V1) is configured to prevent the methanol from being reversed through the transesterification of 1,3-propanediol and dimethyl terephthalate in the lower kneader reactor to prevent the reverse reaction by methanol. At this time, by using the control valve of the outlet (K-V1) to block the connection between the kneader-type extruder and the vacuum pump and to control the methanol to be vented to the outside (Vent). As the transesterification reaction proceeds, a low molecular weight poly (trimethylene terephthalate) is produced, and when the conversion rate of the raw material with the viscosity inside the reactor reaches 70% or more and less than 95%, a stabilizer and an additive are added to the raw material inlet. To polycondensation reaction of low molecular weight poly (trimethylene terephthalate). At this time, by using a control valve of the outlet (K-V1) to adjust the connection to the kneader-type extruder and the vacuum pump to adjust the vacuum to be maintained inside the kneader-type extruder. Operation conditions under which the polycondensation reaction proceeds are performed in the same manner as the operation conditions of the second half of the extruder type reactor P2 of FIG. 1. The final polymer produced through the kneader extruder is pelletized using a water-cooled pelletizer connected directly to the die of the extruder, followed by dehydration and drying to prepare the final product.

In the above embodiments, the reactor or kneader type extruder is limited to the case of an extruder type equipped with one or two extruder type screws, but various other types of reactors including a stirrer type reactor are provided within the scope of the present invention. It is also possible to use reactors of the type.

According to the manufacturing process of the simplified poly (trimethylene terephthalate) (PTT) according to the present invention, it is possible to efficiently mass-produce poly (trimethylene terephthalate) (PTT).

1 is a process schematic diagram of manufacturing poly (trimethylene terephthalate) using one extruder type reactor equipped with a separation controller,

2 is a process schematic diagram of connecting two extruder reactors without a separation controller in series to produce poly (trimethylene terephthalate),

3 is a process schematic diagram of preparing poly (trimethylene terephthalate) using a kneader extruder.

Claims (11)

In the method for producing poly (trimethylene terephthalate) (PTT), The reactor is divided into two parts, the first half (P1) and the second half (P2) by the separation control device (S), there is a raw material inlet (F11) and outlet (V11) in the first half of the reactor (P1), the second half of the reactor (P2) At least one auxiliary inlet (F12) is mounted on the reactor using a reactor consisting of at least one connection (V12) connected to the vacuum pump, i) feeding 1,3-propanediol and terephthalic acid to the feed inlet (F11) of the first half of the reactor (P1) such that the molar ratio of 1,3-propanediol to terephthalic acid is between 1.1 and 2.2; ii) producing low molecular weight poly (trimethylene terephthalate) by direct esterification in the first half of the reactor (P1); iii) A high molecular weight poly (trimethylene terephthalate) is produced by polycondensation reaction while supplying the transesterification catalyst and the additive to the auxiliary inlet (F12) of the second half of the reactor (P2) and applying vacuum to the second half of the reactor (P2). Making; And iv) pelletizing using a pelletizer directly connected to the reactor; Poly (trimethylene terephthalate) manufacturing method comprising a. In the method for producing poly (trimethylene terephthalate) (PTT), The reactor is divided into two parts of the first half (P1) and the second half (P2) by the separation control device (S), the raw material inlet (F11) and outlet (V11) in the first half of the reactor (P1), the second half of the reactor (P2) By using a reactor configured with at least one auxiliary inlet (F12) and one or more connections (V12) connected to the vacuum pump, i) 1,3-propanediol and terephthalic acid are fed to the feed inlet (F11) of the first half of the reactor (P1) so that the molar ratio of 1,3-propanediol to terephthalic acid is 1.1 to 2.2, and the transesterification catalyst is fed to the feed inlet. Supplying; ii) producing low molecular weight poly (trimethylene terephthalate) by direct esterification in the first half of the reactor (P1); iii) supplying the additive to the auxiliary inlet (F12) of the second half of the reactor (P2), and producing a high molecular weight poly (trimethylene terephthalate) by polycondensation reaction while applying a vacuum to the second half of the reactor (P2); And iv) pelletizing using a pelletizer directly connected to the reactor; Poly (trimethylene terephthalate) manufacturing method comprising a. In the method for producing poly (trimethylene terephthalate) (PTT), The reactor is divided into two parts, the first half (P1) and the second half (P2) by the separation control device (S), there is a raw material inlet (F11) and outlet (V11) in the first half of the reactor (P1), the second half of the reactor (P2) At least one auxiliary inlet (F12) is mounted on the reactor using a reactor consisting of at least one connection (V12) connected to the vacuum pump, i) 1,3-propanediol and dimethyl terephthalate are fed to the feed inlet (F11) of the first half of the reactor (P1) so that the molar ratio of 1,3-propanediol to dimethyl terephthalate is 1.1 to 2.2, and transesterification Supplying a catalyst to the raw material inlet (F11); ii) producing low molecular weight poly (trimethylene terephthalate) by transesterification in the front half of the reactor (P1); iii) supplying the additive to the auxiliary inlet (F12) of the second half of the reactor (P2), and producing a high molecular weight poly (trimethylene terephthalate) by polycondensation reaction while applying a vacuum to the second half of the reactor (P2); And iv) pelletizing using a pelletizer directly connected to the reactor; Poly (trimethylene terephthalate) manufacturing method comprising a. The method according to any one of claims 1 to 3, Viscosity separation control device installed between the first half of the reactor (P1) and the second half of the reactor (P2) when the raw material introduced into the first half of the reactor (P1) is converted to 70% or more and less than 95% to low molecular weight poly (trimethylene terephthalate) Method of producing a poly (trimethylene terephthalate), characterized in that for moving the reactant to the second half (P2) of the reactor by operating the switch. The method of claim 4, wherein The reactor is a poly (trimethylene terephthalate) production method characterized in that the extruder type reactor is equipped with one or two extruder type screw therein. The method according to any one of claims 1 to 3, The reactor is a poly (trimethylene terephthalate) production method characterized in that the inside is an extruder type reactor equipped with one or two extruder type screw. In the method for producing poly (trimethylene terephthalate) (PTT), Two reactors (R1, R2) are connected in series, the first reactor (R1) is equipped with a raw material inlet (F21) and outlet (V21), the second reactor (R2) has a secondary inlet (F22) 1 By using a reactor in which two or more reactors, each of which is equipped with at least one connection unit V22 connected with a vacuum pump, are connected in series, i) feeding 1,3-propanediol and terephthalic acid to the feed inlet (F21) of the first reactor (R1) such that the molar ratio of 1,3-propanediol to terephthalic acid is between 1.1 and 2.2; ii) producing low molecular weight poly (trimethylene terephthalate) by direct esterification in the first reactor (R1); iii) The resulting low molecular weight poly (trimethylene terephthalate) is transferred to the second reactor (R2) and simultaneously fed with a transesterification catalyst and additives, and by polycondensation reaction while applying vacuum to the second reactor (R2). Producing high molecular weight poly (trimethylene terephthalate); And iv) pelletizing using a pelletizer directly connected to a second reactor (R2); Poly (trimethylene terephthalate) manufacturing method comprising a. In the method for producing poly (trimethylene terephthalate) (PTT), Two reactors (R1, R2) are connected in series, the first reactor (R1) is equipped with a raw material inlet (F21) and outlet (V21), the second reactor (R2) has a secondary inlet (F22) 1 By using a reactor in which two or more reactors, each of which is equipped with at least one connection unit V22 connected with a vacuum pump, are connected in series, i) 1,3-propanediol and dimethyl terephthalate are fed to the feed inlet (F21) of the first reactor (R1) so that the molar ratio of 1,3-propanediol to dimethyl terephthalate is 1.1 to 2.2, and transesterification Supplying a catalyst to the raw material inlet (F21); ii) producing low molecular weight poly (trimethylene terephthalate) by transesterification in the first reactor (R1); iii) The low molecular weight poly (trimethylene terephthalate) produced is delivered to the second reactor (R2) and at the same time, the additive is supplied, and the high molecular weight poly (tree) is Methylene terephthalate); And iv) pelletizing using a pelletizer directly connected to a second reactor (R2); Poly (trimethylene terephthalate) manufacturing method comprising a. The method according to claim 7 or 8, The reactors (R1, R2) connected in series is an extruder type reactor equipped with one or two extruder type screws therein, characterized in that the poly (trimethylene terephthalate) manufacturing method. In the method for producing poly (trimethylene terephthalate) (PTT), A kneader extruder equipped with a raw material inlet (K-F1) and an outlet (K-V1), the outlet (K-V1) is a kneader configured to be connected to an external or vacuum pump through a control valve. Using the extruder) i) feeding 1,3-propanediol and terephthalic acid to the feed inlet (K-F1) such that the molar ratio of 1,3-propanediol to terephthalic acid is between 1.1 and 2.2; ii) producing low molecular weight poly (trimethylene terephthalate) by direct esterification; iii) supplying the transesterification catalyst and the additive to the raw material inlet (K-F1), and applying a vacuum to the kneader extruder to produce a high molecular weight poly (trimethylene terephthalate) by polycondensation; And iv) pelletizing using a pelletizer directly connected to the kneader extruder; Process in a batch to produce poly (trimethylene terephthalate). In the method for producing poly (trimethylene terephthalate) (PTT), A kneader extruder equipped with a raw material inlet (K-F1) and an outlet (K-V1), the outlet (K-V1) is a kneader configured to be connected to an external or vacuum pump through a control valve. Using the extruder) i) 1,3-propanediol and dimethyl terephthalate are fed to the raw material inlet (K-F1) so that the molar ratio of 1,3-propanediol to dimethyl terephthalate is 1.1 to 2.2, and the transesterification catalyst and additives Supplying the inlet (K-F1); ii) producing low molecular weight poly (trimethylene terephthalate) by transesterification reaction; iii) subjecting the kneader extruder to vacuum to form a high molecular weight poly (trimethylene terephthalate) by polycondensation; And iv) pelletizing using a pelletizer directly connected to the kneader extruder; Process in a batch to produce poly (trimethylene terephthalate).

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