RU2666863C1 - Exchange reaction system, production system of modified polyester containing the same method of modified polyester production, and product as modified polyester fiber - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: invention relates to a system for exchange reactions, modified polyester production system, modified polyester manufacturing method, and modified polyester fiber produced by this method. Exchange reaction system comprises vertical reactor (2) with a fully mixed flow located on the top wall of vertical reactor (7) with a piston flow. Modified polyester production system comprises an esterification system, pre-polycondensation system, final polycondensation system and modifier addition system, which is located between the systems of esterification and pre-polycondensation. Method for producing modified polyester comprises stages of preparing a slurry and modifier, adding the slurry to the modified polyester production system and adding the modifier to the modified polyester production system. Modified polyester fiber obtained by this method has a specific breaking load of 2.5 cN/dtex to 6.0 cN/dtex, a tensile strength of 20 % to 50 %, and a dye homogeneity of 4 to 5 grades.EFFECT: simplicity of control over the conditions of exchange reactions is provided, the cost of production of modified polyester is reduced, the time of the production cycle is shortened, and the homogeneity of the polyester structure is increased.21 cl, 4 dwg, 1 tbl, 18 ex

Description

Technical field

The present invention relates to the field of synthesis of high molecular weight materials and, in particular, relates to an exchange reaction system, a modified polyester production system containing the same method for producing a modified polyester and a product in the form of a modified polyester fiber.

State of the art

Polyester, as one of the most important chemical synthetic materials, is widely used in such fields as the production of fibers, containers, engineering plastics, and medical materials. Under the influence of technological progress and market demand, the global polyester industry has developed rapidly in recent years, and competition between similar products is becoming increasingly intense. In light of the new competitive situation and taking into account environmental degradation in the country and abroad, as well as the presence of large excess volumes of traditional varieties of products, the active research of ways of sustainable development of the industry and acceleration of transformations and modernization of polyester products and technologies is of key importance; The development of processes and devices for the production of differentiated polyester products is the main approach to transformation and modernization.

Technologically, the development of differentiated polyester products is mainly carried out in two directions: chemical and physical modification. Chemical modification consists in maintaining the functional modifier in the structure of the polyester molecule to form a copolymer, and physical modification consists in homogeneous mixing of the functional modifier with the polyester matrix, as a result of which a mixture is formed, this is done to give the polyester certain physical properties, for example, hygroscopicity, fire resistance, antibiotic properties, electrical conductivity or cationic coloring ability of a cationic dye. Highly effective dispersion of the modifier and accuracy control of the proportions of the added components are the key to ensuring the stability of the production of differentiated polyesters and the uniformity of the product structure.

Currently, before the polycondensation process, a mixing device consisting of an esterification reactor and a tubular static oligomer mixer is usually used for mixing and dispersing the modifier in the main material, and neither of the two devices has the ability to destroy the material and make it homogeneous , so it is difficult to achieve uniform mixing of the base material and the incompatible modifier, which ultimately leads to less uniformity of the structure of the modifier polyester, and spinning fibers are prone to chromatic aberration during dyeing. Therefore, improving the uniformity of the structure of the modified polyester has become an urgent task that must be addressed.

Disclosure of invention

The present invention is intended to provide an exchange reaction system, a modified polyester production system comprising the same method for producing the modified polyester and fiber product from the modified polyester in order to increase the uniformity of the structure of the modified polyester.

To solve the aforementioned problem, in accordance with one aspect of the present invention, there is provided an exchange reaction system comprising: a vertical reactor with a fully mixed stream, comprising a first material inlet and a first material outlet provided thereon, and a piston vertical reactor with a second inlet for material, and a second material outlet provided therein; moreover, a vertical complex reactor with a mixed flow is provided on the upper wall of the vertical reactor with a piston flow, and the first outlet for the material is connected to the second inlet for the material.

Also, the bottom wall of a fully mixed flow vertical reactor is at least partially shared with the top wall of the piston flow vertical reactor in order to form a common reactor wall, and the first material outlet and the second material inlet are overlapped and located on a common the wall of the reactor.

Also, the common wall of the reactor has a structure in which the middle part is immersed downward relative to the vertical reactor with a fully mixed flow.

Also, the vertical fully mixed flow reactor and the vertical reciprocating flow reactor are coaxial, and preferably, the first material outlet and the second material inlet are overlapped and located on the axis of the fully mixed flow vertical reactor and the vertical piston flow reactor.

Also, a vertical fully mixed flow reactor has a length to diameter ratio of 0.5 to 3, a vertical piston flow reactor has a length to diameter ratio of 2 to 20, and a vertical fully mixed flow reactor has a diameter greater than the diameter of a vertical piston reactor flow; and, more preferably, the diameter of the vertical reactor with a fully mixed stream is from 1.05 to 5 diameters of a vertical reactor with a piston stream.

The exchange reaction system also further comprises a cascade control system for the liquid level, comprising: a liquid level sensor used to determine liquid level information inside a fully mixed flow vertical reactor and send a liquid level signal in accordance with the liquid level information; and an electric control valve located on the communication pipe between the first material outlet in the vertical reactor with fully mixed flow and the second material inlet in the vertical reactor with piston flow, and is used to receive a signal about the liquid level and to adjust the degree of opening of the electric control valve .

Also, a fully mixed flow vertical reactor comprises a first reactor vessel and a mixing device, comprising: a mixing rod connected to the first reactor vessel, one end extending into the interior of the first reactor vessel; a set of mixing blades located in the axial direction symmetrically or radially on the mixing rod; preferably, the mixing device containing a set of groups of mixing blades, is parallel to the direction of extension of the mixing rod, each of the groups of mixing blades contains a set of mixing blades located on the same horizontal plane, and, more preferably, the number of groups of mixing blades is from 2 to 5, and more preferably, various mixing blades in two adjacent groups of mixing blades alternate.

Also, a fully stirred flow vertical reactor further comprises an internal set of spiral heating pipes, the internal set of spiral heating pipes being located inside the first reactor vessel and surrounds the mixing device; and preferably, the internal set of spiral heating pipes contains several groups of internal spiral heating pipes arranged in concentric circles, each of the internal spiral heating pipes being axially and spiral along a fully mixed flow vertical reactor.

Also, the vertical reciprocating flow reactor comprises a second reactor vessel and a prefabricated film supply unit located inside the second reactor vessel; this film supply unit assembly comprising several film supply units arranged in parallel layers; preferably, the film supply unit assembly contains 4 to 40 layers of film supply units.

Also, the film supply unit comprises: a porous cover; an overflow tray located further downstream of the porous lid in the material stream, the overflow tray provided with an overflow hole; preferably, the porous cover has a structure with the center raised up, the overflow tray overflow hole is located in the center of the bypass tray, and even more preferably, the porous cover is a conical plate in the form of an umbrella.

In accordance with another aspect of the present invention, there is further provided a modified polyester production system comprising an esterification system, a preliminary polycondensation system and a final polycondensation system, the modified polyester production system further comprising an in-line modifier adding system located between the esterification system and the preliminary polycondensation system in accordance with the order material consumption and any system of exchange reactions, as in omyanuto above.

Also, the in-line modifier adding system comprises an in-line injection device of a modifying superconcentrate and / or a in-line injection device of a modifying superconcentrate; preferably, the modulating superconcentrate inline injection device comprises a modifying superconcentrate drying system, a screw extruder and a metering pump for melt the modifying superconcentrate, which are connected in series; and the modifier solution in-line injection device comprises a reservoir for preparing a modifier solution, a reservoir for supplying a modifier solution, a dosing pump of a modifier solution and an injector of the modifier solution, which are connected in series.

Also, the modified polyester production system further comprises a dynamic mixer located between the in-line modifier adding system and the exchange reaction system; preferably, the dynamic mixer is a 1-5 stage high shear dynamic mixer.

Also, the modified polyester production system further comprises an oligomeric heat exchanger and an oligomer dispensing device that are arranged in a material flow sequence between the esterification system and an in-line addition system, preferably the oligomer delivery dispensing device comprises an oligomer pump and an oligomer flow meter located downstream of the oligomer pump.

In accordance with another aspect of the present invention, there is provided a method for manufacturing a modified polyester comprising the following steps: respectively, preparing a suspension and a modifier; and adding a slurry to any modified polyester production system as mentioned above, and adding a modifier to the in-line system for adding any modified polyester production system as mentioned above, for the purpose of producing the modified polyester.

Also in the production process of the modifier receive a modifier having a dynamic viscosity of from 0.05 Pa⋅s to 1000 Pa⋅s.

Also, when the modified polyester production system comprises an oligomeric heat exchanger, the oligomeric heat exchanger adjusts the oligomer temperature to 180 ° C to 300 ° C; and, when the modified polyester production system comprises a dynamic mixer, the dynamic mixer has a rotation speed of 50 rpm to 5000 rpm.

Also, the exchange reaction system has a reaction temperature from 180 to 300 ° C. and a reaction time from 10 minutes to 180 minutes.

Also, the molten prepolymer obtained from the preliminary polycondensation system has a characteristic flow viscosity of 0.10 to 0.50 dl / g; and preferably, the final polymer melt obtained from the final polycondensation system has an inherent flow viscosity of 0.50 dl / g to 1.50 dl / g.

In accordance with another aspect of the present invention, there is provided a modified polyester fiber product obtained from a modified polyester fiber obtained in any system for producing a modified polyester fiber product, as mentioned above.

The modified polyester fiber product also has a specific tensile load of 2.5 CN / dtex to 6.0 CN / dtex, a tensile elongation of 20% to 50%, and dye uniformity of 4 to 5.

Using the technical solution in accordance with the present invention, this exchange reaction system of such a directly connected design, where a vertical reactor with a fully mixed flow is provided on the upper wall of a vertical reactor with a piston flow, can provide an opportunity for the material after it is effectively mixed in a vertical a reactor with a fully mixed flow, quickly and conveniently flow into a vertical reactor with a piston flow under the action of gravity, which is significantly juice It saves the time of material transfer from a vertical reactor with a fully mixed stream to a vertical reactor with a piston stream so that the material in a state close to uniform after an exchange reaction in a vertical reactor with a completely mixed stream can be transferred at an earlier stage to a vertical reactor with a piston stream for the subsequent exchange reaction in a state close to homogeneous, which makes it easy to control the conditions of the exchange reaction; in addition, the uniformity of the distribution of the modifier in the structure of the polyester molecules can be improved, and thus the resulting modified polyester is structurally highly homogeneous, and the system is suitable for the production of high-quality fiber and film products.

Brief Description of the Drawings

The accompanying drawings, which form part of the description, are attached to the present invention and are necessary for further understanding thereof, and illustrative examples of the present invention and their descriptions are used to explain the present invention and do not constitute an incorrect definition of the present invention.

In the drawings

in FIG. 1 shows a metabolic reaction system represented by a typical embodiment in accordance with the present invention;

in FIG. 2 shows a process flow of a modified polyester production system provided in a typical embodiment in accordance with the present invention;

in FIG. 3 shows a modified polyester production system represented by a typical embodiment in accordance with the present invention; as well as

in FIG. 4 shows DSC scan curves of the modified polyesters obtained in Embodiment 1 of the present invention and Comparative Embodiment 1 of the present invention.

Detailed Description of Embodiments

It should be noted that embodiments of the invention and features in embodiments of the invention in this application can be combined with each other without conflict. The present invention will now be described in detail with reference to the accompanying drawings and in combination with embodiments of the invention.

As mentioned in the “Background” section, there is a technical problem in the prior art in that it is difficult to use uniformity with the base material when using an incompatible modifier, which leads to lower uniformity of the structure of the modified polyester. In order to eliminate the aforementioned defects of the prior art, the present invention provides an exchange reaction system as shown in FIG. 1, which comprises: a vertical reactor 2 with a fully mixed flow, comprising a first material inlet and a first material outlet and a piston vertical reactor 7 that comprises a second material inlet and a second material outlet; moreover, a vertical reactor with a fully mixed flow is provided on the upper wall of the vertical reactor with a piston flow, and the first material outlet is connected to the second material inlet.

With the above-mentioned exchange reaction system in accordance with the present invention, this exchange reaction system is of such a directly connected design, where a vertical reactor with a fully mixed flow is provided on the upper wall of a vertical reactor with a piston flow, whereby the material, having reached the state of efficient mixing in a vertical reactor with a completely mixed flow, can quickly and conveniently flow into a vertical reactor with a piston flow under the action of gravity, which significantly reduces the transition time of a material from a vertical reactor with a fully mixed stream to a vertical reactor with a piston stream so that the conditions of an almost homogeneous exchange reaction of the material in a vertical reactor with a completely mixed stream at an earlier stage can be transferred to a vertical reactor with a piston stream for subsequent close to homogeneity of the exchange reaction, which makes it easy to control the conditions of the exchange reaction; the uniformity of the distribution of the modifier in the structure of the polyester molecules can also be improved, and thus the resulting modified polyester is structurally highly homogeneous, and the system is suitable for the production of high-quality fiber and film products.

Said exchange reaction system in accordance with the present invention provides a direct connection between two reaction reactors by placing a vertical reactor 2 with a fully mixed stream on the upper wall of a vertical piston flow reactor. Compared to two reaction reactors connected through a pipe, the reaction conditions in this directly connected exchange reaction system are easily controlled. In order to further optimize the design, the portions of the lower wall of the vertical fully mixed flow reactor and the vertical reciprocating flow reactor can be separated to form a common wall, and the first material outlet and the second material inlet are overlapped and arranged on a common wall. This one-piece exchange reaction system not only reduces production costs, but also reduces the cycle of material flow between a vertical reactor with a fully mixed stream and a vertical reactor with a piston stream, so that the material after uniform mixing can be quickly introduced into a vertical reactor with a piston stream, this ensures uniform distribution of the modifier in the structure of polyester molecules.

In the aforementioned exchange reaction system in accordance with the present invention, the common wall of a vertical fully mixed flow reactor and a vertical reciprocating flow reactor is so designed that the middle part is sunk down relative to the fully mixed vertical flow reactor, and such a downwardly inclined design facilitates a soft flow of material over its entire volume, when it flows out of the first outlet of the material, entering a vertical reactor with a piston flow, thus Zoom supported relative uniformity of the material throughout the volume.

In a preferred embodiment of the present invention, in the said exchange reaction system, the vertical fully mixed flow reactor and the vertical reciprocating flow reactor are coaxial, and this coaxial arrangement method increases the stability of the design of the exchange reaction system and reduces the space requirements for the installation.

When comprehensively considering the optimization effects of the degree of mixing and the residence time of the material in the exchange reaction in the said exchange reaction system in accordance with the present invention, preferably the vertical reactor 2 with a fully mixed flow has a length to diameter ratio of 0.5 to 3, the vertical reactor 7 with a piston the flow has a ratio of length to diameter from 2 to 20, and the diameter of the vertical reactor 2 with a fully mixed flow is larger than the diameter of the vertical reactor 7 with a piston flow; and, more preferably, the diameter of the vertical reactor 2 with a fully mixed stream is from 1.05 to 5 diameters of the vertical reactor 7 with a piston flow. When a vertical reactor with a fully mixed stream has a length to diameter ratio in the above range, it is advisable that when mixing the material becomes more uniform throughout its volume without zones not affected by mixing; and a vertical reciprocating flow reactor using a length to diameter ratio in said range has a tower structure in which a ratio of large diameter to small diameter can increase the potential difference and facilitates the flow of material under its own weight into the reactor from top to bottom.

On this basis, the diameter of the vertical reactor 2 with a fully mixed flow is larger than the diameter of the vertical reactor 7 with a piston flow; and more preferably, when the diameter of the vertical reactor 2 with a fully mixed flow is from 1.05 to 5 diameters of the vertical reactor 7 with a piston flow, the advantage being not only in the large diameter, the low ratio of length to diameter in a vertical reactor with a fully mixed flow is The advantage is that with stirring the material becomes more uniform throughout its volume without untreated zones, but the following points are also an advantage: vertical reaction a piston flow chamber using a tower-like construction with a small diameter and high length to diameter ratio allows to increase the potential difference, which facilitates the flow of material under its own weight into the reactor from top to bottom; In addition, space is saved for the installation.

In order to have the material mixed in the vertical reactor with a fully mixed stream more fully, in a preferred embodiment of the present invention, said exchange reaction system further comprises a cascaded liquid level control system comprising: a liquid level sensor used to determine liquid level information inside a fully mixed vertical vertical reactor flow and send a signal about the liquid level in accordance with the liquid level; and an electric control valve located on the communication pipe between the first material outlet in the vertical reactor with fully mixed flow and the second material inlet in the vertical reactor with piston flow, and is used to receive a signal about the liquid level and to adjust the degree of opening of the electric control valve . The liquid level in a vertical reactor with a fully mixed flow is measured in real time using the aforementioned liquid level sensor, and when the liquid level changes, the electric signal controls the degree of opening of the electric control valve to ensure the effective operation of the vertical reactor with a fully mixed flow and efficient and uniform mixing of the material .

In the aforementioned exchange reaction system in accordance with the present invention, the liquid level, i.e. the position of the liquid surface, in a vertical reactor with a completely mixed flow is determined depending on the holding time required for the exchange reaction of the mixture of modifier and polyester oligomer to form a homogeneous liquid. In industrial applications, the liquid level in a fully mixed flow vertical reactor can be reasonably adjusted depending on the required holding time.

In the aforementioned exchange reaction system in accordance with the present invention, a vertical fully mixed flow reactor is generally aimed at achieving complete mixing of the material, and therefore all vertical fully mixed flow reactors that are capable of performing the said function are applicable to the present invention. In the present invention, said fully mixed flow vertical reactor comprises a first reactor vessel and a mixing device, the mixing device mixing the material, thereby ensuring efficient and uniform mixing of the material. In the present invention, the stirring device used comprises a stirring bar 5 connected to the first reactor vessel, with one end extending toward the inside of the first reactor vessel; and a plurality of mixing blades 6 arranged axially symmetrically or radially on the mixing rod 5. The mixing rod 5 is connected to the first reactor vessel and is driven by an electric motor located outside the first reactor vessel.

Preferably, the plurality of mixing blades 6 are arranged symmetrically in the axis or symmetrically in radius on the stirring bar 5 to ensure uniform mixing and efficient uniform mixing of the material in the first reactor vessel in accordance with the desired mixing intensity. The mixing blades 6, arranged according to the aforementioned scheme in accordance with the present invention, have a strong mixing effect, can turn the modifier into a material uniformly dispersed in the polyester oligomer up to the micro level, so that the exchange reaction between the polyester oligomer and the modifier is close to a homogeneous reaction, which increases the rate of the metabolic reaction, reduces the reaction time and effectively limits the occurrence of side reactions, such as thermal decomposition of the modifier.

In the aforementioned preferred embodiment, the stirring device also preferably comprises a plurality of mixing paddle groups arranged in parallel in the direction of extension of the stirring bar 5, each of the paddle mixing groups containing a plurality of mixing paddles 6 located on the same horizontal plane to achieve uniform mixing material such as a fully mixed stream at different values of the liquid level and at the same liquid level. In industrial applications, the amount of said mixing paddle groups can, as a rule, be appropriately adjusted depending on the amount of material to be processed. In the present invention, the number of said mixing blade groups is preferably from 2 to 5. It is more preferable that the various mixing blades 6 in the two adjacent mixing blade groups alternate, which allows the process to flow through two adjacent mixing blade groups relatively longer, which gives a better effect mixing and also provides a reduction in adverse reactions.

In the above-mentioned exchange reaction system in accordance with the present invention, there are no special requirements for heating equipment inside a vertical reactor with a fully mixed flow, if it can provide the reaction temperature required for the material. In a preferred embodiment of the present invention, said fully stirred flow vertical reactor further comprises an internal set of spiral heating tubes, in which an internal set of spiral heating tubes is located inside the first reactor vessel and surrounds the stirring device. Since the inner set of spiral heating pipes surrounds the stirring device, it is possible to maintain a relatively uniform temperature of the material with stirring and mixing in order to achieve uniform mixing so that the exchange reaction at an early stage is close to the conditions of a homogeneous reaction.

In the above embodiment, it is also preferable that the internal set of spiral heating pipes comprises several groups of internal spiral heating pipes arranged in concentric circles, each of the internal spiral heating pipes being axially and spirally along a vertical mixed flow reactor. With this arrangement, the material is heated more evenly in the radial and axial directions. In said internal spiral heating pipes in accordance with the present invention, an independent system with a secondary coolant is used, and by controlling the temperature and flow rate of the coolant in the internal spiral heating pipes, the reaction temperature of the material of the reaction system can be quickly controlled, so that the occurrence of a side effect of thermal degradation of the modifier is effectively limited.

In the above-mentioned exchange reaction system in accordance with the present invention, a simple known piston flow reactor of the prior art can be used as a vertical reciprocating flow reactor if it can provide a mixing effect of a piston flow type for the material. In a preferred embodiment of the present invention, said vertical reciprocating flow reactor includes a second reactor vessel and an assembly of a film supply unit located inside the second reactor vessel; and a film supply unit assembly comprising several film layers of a film supply unit 12 arranged in parallel.

As mentioned above, by providing a plurality of layers of the film supplying units 12 in the second reactor vessel, the homogeneous liquid generated during the exchange reaction at an earlier stage enters the lower layer of the vertical reactor with a piston flow under the action of a pressure difference, then passes through the film supplying assembly consisting of several layers of the film supply unit 12, under its own weight, and flows downward in the piston flow mode, and in the flow of this type the reaction material can reach the first inlet and first outlet bottom holes. Therefore, by controlling the reaction temperature and the holding time of the material in a vertical reciprocating flow reactor, the reaction mixture can be effectively controlled to obtain a structurally homogeneous modified polyester oligomer.

In the aforementioned embodiment of the present invention, the holding time of the material in the reaction stream can be adjusted by setting the number of layers of the film supply unit 12 provided in the vertical piston flow reactor. The larger the number of layers of the film supply unit 12, the smaller the difference in the holding time between the materials and the more uniform the exchange reactions occur. In the present invention, it is preferable that the film supply unit assembly contains from 5 to 60 layers of the film supply unit 12 and, more preferably, from 10 to 30 layers.

In a preferred embodiment of the present invention, the film supply unit 12 in said vertical reciprocating flow reactor comprises a porous cover 8 and a bypass tray 9, the bypass tray 9 being located upstream of the porous cover 8, in the bypass tray 9 there is a bypass hole. The porous cover 8 can cut the flow of material and acts as a static mixer. In a more preferred embodiment of the present invention, said porous cover 8 is designed so that its center is raised up, which facilitates the spreading of the material flow in the direction of the peripheral portions. The overflow hole of the bypass tray 9 is located in the center of the bypass tray 9, and thanks to this arrangement method, the material flows more easily under its own weight to the porous cover 8 of the next film supply unit 12, and then the material is very quickly distributed around the periphery of the porous cover.

In the aforementioned preferred embodiment, the porous cover 8 is preferably an umbrella-shaped conical plate, and a tapering umbrella plate having a certain taper facilitates the flow of material from the bypass tray 9 of the previous layer of the film supply unit 12 to the center of the conical umbrella plate of the next layer of the film supply unit 12, after which the material can quickly drain under the action of gravity to the peripheral portions of the lid. Specifically, the overflow hole of the bypass tray 9 faces the top of the conical umbrella plate, so that material flowing from the bypass tray 9 to the top of the conical umbrella plate will more quickly drain under gravity along the umbrella plate, which has a certain taper, towards the peripheral portions .

In another exemplary embodiment of the present invention, there is further provided a modified polyester production system, in a flow diagram of a modified polyester production process as shown in FIG. 2, it can be seen that this modified polyester production system further comprises an in-line modifier addition system that is installed between the esterification system and the preliminary polycondensation system in accordance with the material flow order and any exchange reaction system, as mentioned above, in addition to the esterification system, the system pre-condensation and the final polycondensation system, which are commonly used in polyester manufacturing processes.

By introducing the in-line modifier adding system and any exchange reaction system, as mentioned above, into the general polyester production system, said modified polyester production system provided by the present invention not only can add the modifier to the polyester oligomer, but can also allow the introduction of the modifier and the polyester oligomer in the exchange reaction, thereby ensuring uniform distribution of the modifier in the structure of the polyester oligomer, so of modified polyester fiber obtained is very homogeneous in structure and can be used for the production of high fiber and film products.

In the aforementioned modified polyester production system of the present invention, the in-line modifier adding system is an in-line system for adding the desired modifier to the polyester oligomer obtained by the esterification reaction and sent from the esterification system. In the production applications of the present invention, the well-known in-line modifier adding system in accordance with the present invention can be applied after proper adjustment depending on the difference of the added modifier. In a preferred embodiment of the present invention, as shown in FIG. 3, an in-line modifier addition system comprises an in-line injection device of a modifying superconcentrate and / or an in-line injection device of a modifier solution. The in-line injection device of the modifying superconcentrate can perform real-time addition of a modifier consisting of solid particles, and the in-line injection device of the modifier solution can perform in-line addition of the modifier in the form of a liquid solution; it is also ensured that both of the in-line modifier injection devices can simultaneously add two or more liquid and solid modifiers.

In the above embodiment of the present invention, the flow injection device of the modifying superconcentrate can be obtained by intelligently adjusting the existing device for in-line adding a solid modifier if it is capable of performing the in-line addition of the desired solid dispersed modifier. For the same reason, with respect to the flow injection device of the modifier solution, an existing liquid flow modifier injection device may be applied to the present invention if necessary adjustment has been made. In a more preferred embodiment of the present invention, said modifying superconcentrate inline injection device comprises a modifying superconcentrate drying system, a screw extruder and a metering pump for modifying the superconcentrate melt, which are connected in series; and the modifier solution in-line injection device comprises a reservoir for preparing a modifier solution, a reservoir for supplying a modifier solution, a dosing pump of a modifier solution and an injector of the modifier solution, which are connected in series.

The modifying superconcentrate inline injection device having the above construction in accordance with the present invention can provide an efficient connection between the modifying superconcentrate production process and the device to which the modifier is to be added, and can further measure the modifying superconcentrate addition volume in order to maintain the accuracy of the modifier addition. For the same reason, the in-line injection of the modifier solution in the aforementioned preferred embodiment of the present invention can simultaneously realize the formulation, delivery, measurement and precise addition of the desired modifier.

Compared with the prior art, where the dispersion of mixing the modifier in the polyester oligomer is achieved mainly by means of a mixing device and a tubular static oligomeric esterification reactor mixer, said modified polyester production system according to the present invention further comprises a dynamic mixer, as shown in FIG. 3, which performs uniform distribution of the modifier in the polyester oligomer with dynamic stirring, thereby achieving almost uniform physical mixing. In a preferred embodiment of the present invention, said dynamic mixer is a 1-5 step high shear dynamic mixer, and mixing with a high shear dynamic mixer provides better material uniformity compared to conventional dynamic mixers.

In the aforementioned modified polyester production system in accordance with the present invention, it is also possible to estimate the amount of polyester oligomer that can be obtained based on the amount of starting material initially introduced into the esterification system, and then the amount of modifier required. If it is desired to more accurately maintain the amount of polyester oligomer in order to more accurately measure the amount of modifier to be added, the modified polyester production system in accordance with the present invention may further comprise an oligomeric heat exchanger and an oligomer metering device that are located in the material flow sequence between the esterification system and the flow system additions. The oligomeric heat exchanger is able to control the temperature of the polyester oligomer from the esterification system to facilitate the addition and mixing of the modifier. The oligomer metering device is capable of accurately measuring the amount of polyester oligomer to which a modifier is to be added. More preferably, the oligomer delivery metering device comprises an oligomer pump and an oligomer flow meter located downstream of the oligomer pump.

In yet another typical embodiment of the present invention, there is also provided a method for preparing a modified polyester comprising the following steps: respectively, preparing a suspension and a modifier; and adding a slurry to any modified polyester production system, as mentioned above, and adding a modifier to the in-line system for adding any modified polyester production system to produce the modified polyester.

In the aforementioned method for preparing a modified polyester in accordance with the present invention, the preparation is carried out using the aforementioned modified polyester production system, allowing the modifier to be evenly distributed in the structure of the polyester molecules, so that the obtained modified polyester has a highly homogeneous structure and is suitable for the production of high-quality fiber and film products.

In the aforementioned preparation method in accordance with the present invention, the suspension is prepared using dicarboxylic acid and a diol as a raw material in accordance with the conventional method of the prior art. In this method, terephthalic acid is the most common dicarboxylic acid, and at least ethylene glycol, propylene glycol, butylene glycol or cyclohexane dimethanol is used as the diol. The modifier preparation process varies depending on the type of modifier. In a preferred embodiment of the present invention, in the manufacturing process of the modifier receive a modifier having a dynamic viscosity of from 0.05 Pa · s to 1000 Pa · s. In preparation, the preferred dynamic viscosity of the modifier solution is from 0.05 Pa to 5 Pa · s, and the preferred dynamic viscosity of the modifying superconcentrate is from 5 Pa · s to 1000 Pa · s. The modifier in the range of dynamic viscosity can provide uniform mixing with a polyester oligomer using a dynamic mixer.

In the aforementioned preparation method according to the present invention, the reaction temperature of the esterification system is the temperature commonly used in prior art esterification reactions, i.e., from 200 ° C to 280 ° C, and the polymerization degree of the polyester oligomer after the esterification reaction is from 1 to 8. Polyester oligomers that polymerize at a relatively low degree are relatively easy to mix or amenable to copolymerization with a modifier.

In said manufacturing method in accordance with the present invention, when the modified polyester production system comprises an oligomeric heat exchanger, the oligomeric heat exchanger controls the oligomer temperature to 180 ° C to 300 ° C. The oligomer temperature is brought to the mentioned temperature range, so that the temperature of the polyester oligomer can be close to the temperature of the added modifier, and side reactions due to the temperature difference can be reduced.

In said preparation method according to the present invention, when the modified polyester production system comprises a dynamic mixer, the dynamic mixer has a rotation speed of from 50 rpm to 5000 rpm. The rotation speed in the above range allows efficient mixing of the polyester oligomer and the modifier.

In the aforementioned preparation method in accordance with the present invention, the reaction temperature and reaction time are slightly different depending on the materials that are involved in the practical exchange reaction in the exchange reaction system. In a preferred embodiment of the present invention, the temperature of said exchange reaction is from 180 ° C to 300 ° C, and the reaction time is from 10 minutes to 180 minutes. By controlling the temperature and time of the exchange reaction in the above ranges, it is possible to provide a highly effective dispersion of the modifier in the polyester oligomer and an almost homogeneous exchange reaction, so that the modifier is evenly distributed in the structure of the polyester polymer as much as possible. In addition, it is also possible to effectively control the degree of exchange reaction by adjusting the reaction temperature and the holding time of the material in a vertical reciprocating flow reactor in an exchange system to obtain a structurally homogeneous modified polyester oligomer.

In the preparation method according to the present invention, the reaction temperature of the pre-polycondensation system is from 200 ° C to 300 ° C, which is commonly used for the prior polycondensation reaction in the prior art. The prepolymer melt obtained after the structurally homogeneous modified polyester oligomer obtained as a result of the exchange reaction in the preparation method in accordance with the present invention underwent a preliminary polycondensation reaction, has a characteristic flow viscosity of 0.10 to 0.50 dl / g, satisfying the requirements viscosity presented at the stage of final polycondensation; and likewise, in the preparation method of the present invention, the final polycondensation reaction conditions are also general conditions for the final polycondensation reactions in the prior art. In a preferred embodiment of the present invention, the reaction temperature in the final polycondensation system is from 200 ° C to 300 ° C. After the structurally homogeneous modified polyester oligomer obtained by the exchange reaction in the production method in accordance with the present invention was subjected to preliminary polycondensation and final polycondensation, a final polymer melt having a characteristic viscosity in the flow of 0.50 dl / g to 1, is obtained. 50 dl / g, satisfying the viscosity requirements in the subsequent final spinning step.

In another typical embodiment of the present invention, there is further provided a modified polyester fiber product obtained from a modified polyester obtained by any modified polyester production system as mentioned above. The modified polyester fiber product in accordance with the present invention has a specific tensile load of 2.5 CN / dtex to 6.0 CN / dtex, a tensile elongation of 20% to 50% and uniformity of the dye class 4-5, and not only the specific breaking load and elongation at break the fiber can satisfy the requirements for the stage of subsequent twisting, but the fiber also has a higher dye uniformity than modified products from complex polyester fibers obtained from local level the art that indicates that the modified product of polyester fiber provided by the present invention has a high structural uniformity.

The benefits of the present invention will be further described below together with specific embodiments.

It should be noted that in embodiments of the present invention, the preparation of the modified polyester is carried out in accordance with the flow shown in FIG. 2, and carry out an additional flowing step of the modified polyester as shown in FIG. 3, on which a modifier is added and dynamic mixing is performed to form a physical mixture, after which the mixture is introduced into the exchange reaction system, as shown in FIG. 1, to perform an exchange reaction. In FIG. 1 symbol 1 denotes the input for the material for the exchange reaction, symbol 2 denotes a vertical reactor with a completely mixed flow, symbol 3 denotes the internal set of spiral heating pipes, symbol 4 denotes the stirring device motor, symbol 5 denotes the mixing rod, symbol 6 denotes symmetrical mixing blades in the axial direction, the sign 7 marks a vertical reactor with a piston flow, the sign 8 marks a cone-shaped plate in the form of an umbrella, the sign 9 marks a bypass current sign 10 denotes an opening for discharging material to participate in the exchange reaction, a sign 11 designates a device for mixing and sign 12 denotes a film feeding unit.

Embodiment 1

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2964 kg / h to the esterification reaction system consisting of a vertical esterification reactor in order to carry out the esterification reaction at a reaction temperature of 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2470 kg / h.

The oligomer from the esterification reaction system is cooled to 250 ° C using a Sulzer type heat exchanger, after which it enters the dynamic mixer together with the melt of the modifying superconcentrate of polycaprolactam from the flow injection device of the modifying superconcentrate, and the melt of the polycaprolactam superconcentrate has a temperature of 250 ° C during injection, the injection flow rate is 125 kg / h, and the dynamic viscosity is 180 Pa · s, and the process sequence for the injection of superconcentrate polik prolactam is as follows: the polycaprolactam superconcentrate is dried by the drying system of the modifying superconcentrate, melted by a screw extruder and injected into the feed pipe of the dynamic mixer directly through the dosing pump of the melt of the modifying superconcentrate when measuring the flow rate and adjusting it depending on the ratio with the flow rate of the oligomer exiting the dosing device oligomer delivery.

The oligomer and the melt of the polycaprolactone modifying superconcentrate are homogeneously mixed with a 5-stage high shear dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 250 ° C, the rotation speed being 3000 rpm, the length to diameter ratio a vertical reactor with a fully mixed flow of the exchange reaction system is 1.5, the number of mixing paddle groups is 3, the ratio of length to diameter is vert Calne plug-flow reactor is 10, the number of layers of the film feed units is 20 and the diameter of a vertical reactor with a fully-mixed flow is twice the diameter of a vertical reactor with plug flow. The mixture of the oligomer and the melt of the modifying polycaprolactam superconcentrate is subjected to an exchange reaction using an ester in the exchange reaction system to obtain an ethylene terephthalate / caprolactam copolymer and then delivered directly to the preliminary polycondensation system for the preliminary polycondensation reaction, the exchange reaction system having a reaction temperature of 260 ° C. and a reaction time of 90 minutes

The preliminary polycondensation system consists of a vertical polycondensation reactor, the reaction temperature in the preliminary polycondensation reactor is 270 ° C. When the intrinsic viscosity of the prepolymer reaches 0.30 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation reactor is 280 ° C. When the intrinsic viscosity of the final polymer reaches 0.80 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a hydrophilic polyester fiber having a specific tensile load of 4.1 CN / dtex, a tensile elongation of 38%, and a class 5 dye uniformity. The fiber dyeing results show that the molecular segment of the polycaprolactam modifier is uniformly distributed in the structure of the polyester molecules, so that the hydrophilic complex the polyester is structurally uniform, and its dyeing does not have chromatic aberration.

Embodiment 2

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2964 kg / h to the esterification reaction system consisting of a vertical esterification reactor to carry out the esterification reaction at a reaction temperature of 261 ° C. A solution of catalytic antimony acetate at a mass concentration of 3.5% is continuously and uniformly injected into the esterification reactor at a flow rate of 41.5 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2246 kg / h

The oligomer from the esterification system is cooled to 230 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with a solution modified with sodium 5-sulfo-bis (hydroxyethyl) -isophthalate, and a flow injection device of the modifier solution. The mass concentration of the sodium-5-sulfo-bis (hydroxyethyl) -isophthalate solution is 25%, the injection temperature is 90 ° C, the injection speed is 186 kg / h, and the dynamic viscosity is 0.1 Pa⋅s, and the technological sequence of the solution injection sodium 5-sulfo-bis (hydroxyethyl) -isophthalate is as follows: an esterification solution of sodium-5-sulfo-bis (hydroxyethyl) -isophthalate is added to the tank for preparing a modifier solution to prepare a solution having a mass concentration of 25% et ilenglycol, and then the solution is transferred to the reservoir for the supply of the modifier solution due to the potential difference and the dosing pump of the modifier solution is introduced into the supply pipe of the dynamic mixer through the injection nozzle of the modifier solution with the measurement of the flow rate and its regulation depending on the ratio of the flow rate of the oligomer output from the dosing device oligomer delivery.

The oligomer and the sodium-5-sulfo-bis (hydroxyethyl) -isophthalate modifier solution are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 230 ° С, rotation speed is 1000 rpm, the ratio of length to diameter of a vertical reactor with a fully mixed flow of the exchange reaction system is 1, the number of mixing paddle groups is 2, the ratio of length to diameter Vertical, plug-flow reactor is 4, the number of layers of the film feed units is 8, and the diameter of the vertical reactor thoroughly mixed stream 1.2 times greater than the diameter of the vertical plug-flow reactor. A mixture of the oligomer and the sodium-5-sulfo-bis (hydroxyethyl) -isophthalate modifier solution is subjected to transesterification in the exchange reaction system to obtain an ethylene terephthalate / sodium-5-sulfo-bis (hydroxyethyl) -isophthalate copolymer, after which the oligomeric pump is delivered directly to the system preliminary polycondensation for conducting the preliminary polycondensation reaction, wherein the exchange reaction system has a reaction temperature of 235 ° C. and a reaction time of 40 minutes.

The preliminary polycondensation system consists of a vertical polycondensation reactor, and the reaction temperature in the preliminary polycondensation reactor is 260 ° C. When the intrinsic viscosity of the prepolymer reaches 0.15 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 275 ° C. When the intrinsic viscosity of the final polymer reaches 0.50 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a dyeable polyester fiber with a cationic dye, having a specific tensile load of 3.0 CN / dtex, an elongation at break of 32% and uniformity of the dye of class 4.5. The fiber dyeing results show that the sodium-5-sulfo-bis (hydroxyethyl) -isophthalate modifier segment is homogeneously distributed in the structure of the polyester molecules, so that the dyeable polyester with a cationic dye is structurally uniform and does not have chromatic aberration.

Embodiment 3

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2808 kg / h to the esterification reaction system consisting of a vertical esterification reactor to carry out the esterification reaction at a reaction temperature of 260 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 3, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2340 kg / h

The oligomer from the esterification system is cooled to 240 ° C using a multi-tube heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polybutylene terephthalate from the in-line injection device of the modifying superconcentrate, and the melt of the polybutylene terephthalate superconcentrate during injection has a temperature of 240 ° C, the injection speed is 250 kg / 250 kg and the dynamic viscosity is 450 Pa · s, and the technological sequence of injection of polybutylene terephthalate superconcentrate as follows: the polybutylene terephthalate superconcentrate is dried using a modifying superconcentrate drying system, melted with a screw extruder and injected into the feed of the dynamic mixer directly with the melt pump of the modifying superconcentrate when measuring the flow rate and adjusting it depending on the ratio with the flow rate of the oligomer leaving the oligomer .

The oligomer and the melt of the modifying superconcentrate of polybutylene terephthalate are homogeneously mixed with a high-shear 5-speed dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 240 ° C, the rotation speed being 1500 rpm, the length to diameter ratio a vertical reactor with a fully mixed flow of the exchange reaction system is 2, the number of mixing paddle groups is 4, the ratio of length to diameter is ikalnogo plug-flow reactor is 15, the number of layers of the film feed unit is 30, and the diameter of the vertical reactor thoroughly mixed stream 1.5 times greater than the diameter of the vertical plug-flow reactor. The mixture of the oligomer and the melt of the modifying superconcentrate of polybutylene terephthalate is subjected to a transesterification reaction in an exchange reaction system to produce an ethylene terephthalate / polybutylene terephthalate copolymer and then delivered directly to the preliminary polycondensation system for preliminary polycondensation, the exchange reaction system having a reaction temperature of 150 ° C. and a reaction time min

The pre-polycondensation system consists of a vertical first pre-polycondensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 260 ° C and the temperature of the reagent of the second pre-condensation reactor is 265 ° C. When the intrinsic viscosity of the prepolymer reaches 0.40 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation reactor is 270 ° C. When the intrinsic viscosity of the final polymer reaches 0.90 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a polyester dyeable fiber with a disperse dye at normal pressure: it has a specific breaking load of 4.2 CN / dtex, a 45% elongation at break, and a uniformity of class 4.5 dye. The fiber dyeing results show that the molecular segment of the polybutylene terephthalate modifier is homogeneously distributed in the structure of the polyester molecules, so that the polyester fiber dyed with a disperse dye at normal pressure is structurally uniform and its dyeing does not have chromatic aberration.

Embodiment 4

A suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2496 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 265 ° C, and the reaction temperature in the second esterification reactor is 268 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 8, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the second esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2080 kg / h

The oligomer from the esterification system is cooled to 300 ° C using a multi-tube heat exchanger and enters the dynamic mixer together with the melt of the modified superconcentrate of polycyclohexane dimethanol terephthalate from the flow injection device of the modifying super concentrate, the melt of the superconcentrate of polycyclohexane dimethanol terephthalate being injected at a temperature of 500 kg / kg has a temperature of 500 ° C , and the dynamic viscosity is 300 Pa ,s, and the technological sequence of injection of the super-end The nitrate of polycyclohexane dimethanol terephthalate is as follows: the polycyclohexane dimethanol terephthalate superconcentrate is dried using a modifying superconcentrate drying system, melted with a screw extruder and injected directly into the dynamic mixer feed pipe using a melt pump modifying the superconcentrate when measuring the flow rate and the flow rate and its regulation oligomeric dispenser.

The oligomer and the melt of the modifying superconcentrate of polycyclohexane dimethanol terephthalate are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 300 ° С, rotation speed 2000 rpm, length to diameter ratio a vertical reactor with a fully mixed flow of the exchange reaction system is 3, the number of mixing paddle groups is 5, the length ratio diameter vertical plug-flow reactor is 12, the number of layers of the film feed units is 24, and the diameter of the vertical reactor thoroughly mixed stream 1.8 times greater than the diameter of the vertical plug-flow reactor. The mixture of the oligomer and the melt of the modifying superconcentrate of polycyclohexane dimethanol terephthalate is subjected to transesterification in an exchange reaction system to produce an ethylene terephthalate / polycyclohexane dimethanol terephthalate copolymer and then the oligomer pump is delivered directly to the pre-polycondensation system for preliminary polycondensation, and the reaction temperature is 100 ° C .

The pre-polycondensation system consists of a vertical first pre-condensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 295 ° C and the temperature of the reagent of the second pre-condensation reactor is 290 ° C. When the intrinsic viscosity of the prepolymer reaches 0.20 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation reactor is 290 ° C. When the intrinsic viscosity of the final polymer reaches 0.70 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a polyester dyeable fiber with disperse dye at normal pressure: it has a specific tensile load of 4.8 CN / dtex, a tensile elongation of 25%, and class 4 dye uniformity. The fiber dyeing results show that the molecular segment of the polycyclohexanedimethanol-terephthalate modifier is homogeneously distributed in the structure of the polyester molecules, so that the polyester fiber dyed with a disperse dye at normal pressure is structurally uniform, and its dyeing does not have chromium matic aberration.

Embodiment 5

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2784 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 265 ° C, and the reaction temperature in the second esterification reactor is 268 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 6, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the second esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 1820 kg / h

The oligomer from the esterification system is heated to 290 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polyethylene naphthalate from the in-line injection device of the modifying superconcentrate, and the molten superconcentrate of polyethylene naphthalate during injection has a temperature of 290 ° C, the injection speed is 750 kg / h, and the dynamic viscosity is 600 Pa⋅s, and the technological sequence of injection of polyethylene naphthalate superconcentrate looks as follows: masterbatch polyethylene is dried by a dryer system modifier masterbatch melted screw extruder and injected into the feed tube dynamic mixer directly metering pump melt modifier masterbatch when measuring the flow velocity and its regulation depending on the relation with the oligomer flow rate exiting the oligomeric dispenser.

The oligomer and the melt of the modifying superconcentrate of polybutylene naphthalate modifier are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 290 ° С, rotation speed 5000 rpm, length to the diameter of the vertical reactor with a fully mixed flow of the exchange reaction system is 2, the number of mixing paddle groups is 4, the ratio of length to d ametru vertical plug-flow reactor is 20, the number of layers of the film feed units is 40, and the diameter of the vertical reactor thoroughly mixed stream 3 times larger than the diameter of the vertical plug-flow reactor. The mixture of the oligomer and the melt of the modifying superconcentrate of polyethylene naphthalate is subjected to a transesterification reaction in an exchange reaction system to produce an ethylene terephthalate / polyethylene naphthalate copolymer and then delivered directly to the preliminary polycondensation system for preliminary polycondensation, the exchange reaction system having a reaction temperature of 290 ° C and a reaction time of 180 min .

The pre-polycondensation system consists of a vertical first pre-condensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 280 ° C and the temperature of the reagent of the second pre-condensation reactor is 285 ° C. When the intrinsic viscosity of the prepolymer reaches 0.20 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation reactor is 290 ° C. When the intrinsic viscosity of the final polymer reaches 0.65 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a high modulus polyester fiber having a specific tensile load of 6.0 CN / dtex, a tensile elongation of 24% and uniformity of class 4 dye. The results of fiber dyeing show that the molecular segment of the polyethylene naphthalate modifier is uniformly distributed in the structure of the polyester molecules, so that the high modulus complex the polyester is structurally uniform, and its dyeing does not have chromatic aberration.

Embodiment 6

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2784 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 260 ° C, and the reaction temperature in the second esterification reactor is 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 5, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the second esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 1820 kg / h

The oligomer from the esterification system is cooled to 230 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polytrimethylene terephthalate from the flow injection device of the modifying superconcentrate, and the melt of the superconcentrate of polytrimethylene terephthalate at injection has a temperature of 230 ° C, the speed is 750 ° C and the injection speed kg / h, and the dynamic viscosity is 150 Pa⋅s, and the process sequence for the injection of polymetrilent superconcentrate The erephthalate is as follows: the polytrimethylene terephthalate superconcentrate is dried using a modifying superconcentrate drying system, melted with a screw extruder and injected directly into the dynamic mixer feed tube with a modulating superconcentrate melt pump when measuring the flow rate and adjusting it depending on the ratio of the oligomer flow rate leaving the oligomer dispenser.

The oligomer and melt of the modifying superconcentrate of polytrimethylene terephthalate modifier are homogeneously mixed with a 4-stage high-shear dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 230 ° C, the rotation speed is 4000 rpm, the length to the diameter of the vertical reactor with a fully mixed stream of the exchange reaction system is 3, the number of mixing paddle groups is 5, the ratio of s to the vertical diameter of the plug-flow reactor is 18, the number of layers of the film feed units equal to 36, and the diameter of the vertical reactor thoroughly mixed stream 4 times greater than the diameter of the vertical plug-flow reactor. The mixture of oligomer and melt of the modifying superconcentrate of polytrimethylene terephthalate is subjected to transesterification in an exchange reaction system to produce an ethylene terephthalate / polytrimethylene terephthalate copolymer and then delivered directly to the preliminary polycondensation system for preliminary polycondensation with the oligomer pump, and the exchange reaction system has a reaction temperature of min. .

The preliminary polycondensation system consists of a vertical preliminary polycondensation reactor, the reaction temperature in the preliminary polycondensation reactor is 245 ° C. When the intrinsic viscosity of the prepolymer reaches 0.40 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation reactor is 255 ° C. When the intrinsic viscosity of the final polymer reaches 0.95 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a polyester fiber dyed with a disperse dye at normal pressure: it has a specific tensile load of 3.2 CN / dtex, a tensile elongation of 50%, dispersion dye absorption at a normal pressure of 95%, and class 4.5 dye uniformity. The fiber dyeing results show that the molecular segment of the polytrimethylene terephthalate modifier is homogeneously distributed in the structure of the polyester molecules, so that the polyester fiber dyed with a disperse dye at normal pressure is structurally uniform, and its dyeing does not have chromatic aberration.

Embodiment 7

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2964 kg / h to the esterification reaction system consisting of a vertical esterification reactor in order to carry out the esterification reaction at a reaction temperature of 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 7, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2470 kg / h.

The oligomer from the esterification system is heated to 270 ° C using a single-tube heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polyhexamethylene adipamide from the in-line injection device of the modifying superconcentrate, and the melt of the superconcentrate of polyhexamethylene adipamide during injection has a temperature of 270 ° C, the injection speed is 125 kg / 125 kg , and the dynamic viscosity is 250 Pa⋅s, moreover, the technological sequence of injection of polyhexamethylene superconcentrate dipamide is as follows: the polyhexamethylene adipamide superconcentrate is dried using a modifying superconcentrate drying system, melted with a screw extruder and injected into the dynamic mixer feed pipe directly with the modifying superconcentrate melt pump when measuring the flow rate and adjusting it depending on the ratio of the oligomer flow rate leaving the oligomer dispenser.

The oligomer and melt of the modifying superconcentrate of polyhexamethylene adipamide modifier are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 270 ° C, rotation speed 2500 rpm, length to the diameter of the vertical reactor with a fully mixed flow of the exchange reaction system is 1.8, the number of mixing paddle groups is 3, the ratio for us to the diameter of the vertical plug-flow reactor is 15, the number of layers of the film feed units is 30, and the diameter of a vertical reactor with fully kneaded flow 5 times greater than the diameter of the vertical plug-flow reactor. The mixture of oligomer and melt of the modifying superconcentrate of polyhexamethylene adipamide is subjected to an exchange reaction using an ester in the exchange reaction system to obtain an ethylene terephthalate / polyhexamethylene adipamide copolymer and then delivered directly to the preliminary polycondensation system for the preliminary polycondensation reaction, the exchange reaction system having a reaction temperature of 265 ° C and a reaction time of 120 minutes

The pre-polycondensation system consists of a vertical first pre-condensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 265 ° C and the temperature of the reagent of the second pre-condensation reactor is 267 ° C. When the intrinsic viscosity of the prepolymer reaches 0.15 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation reactor is 270 ° C. When the intrinsic viscosity of the final polymer reaches 0.78 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a hydrophilic polyester fiber having a specific tensile load of 4.2 CN / dtex, an elongation of 32% and a uniformity of the dye of class 5. The results of fiber dyeing show that the molecular segment of the polyhexamethylene adipamide modifier is uniformly distributed in the structure of the polyester molecules, so that the hydrophilic complex the polyester is structurally uniform, and its dyeing does not have chromatic aberration.

Option exercise 8

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2808 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 262 ° C, and the reaction temperature in the second esterification reactor is 267 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 6, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the second esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2080 kg / h

The oligomer from the esterification system is heated to 300 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polytetramethylene adipamide from the in-line injection device of the modifying superconcentrate, and the melt of the superconcentrate of polytetramethylene adipamide at the injection temperature is 300 ° C, the speed at 300 ° C, the speed kg / h, and the dynamic viscosity is 1000 Pa⋅s, and the technological sequence of injection of polytetramethyl superconcentrate nadipamide is as follows: a superconcentrate of polytetramethylene adipamide is dried using a modifying superconcentrate drying system, melted with a screw extruder and injected directly into the dynamic mixer feed tube with a modulating superconcentrate melt pump when measuring the flow rate and adjusting it depending on the ratio with the oligomer flow rate leaving the oligomer oligomeric dispenser.

The oligomer and melt of the modifying superconcentrate of polytetramethylene adipamide modifier are homogeneously mixed with a 4-stage high-shear dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 300 ° С, rotation speed 2000 rpm, length to the diameter of the vertical reactor with a fully mixed flow of the exchange reaction system is 3, the number of mixing paddle groups is 4, the ratio of s to the vertical diameter of the plug-flow reactor is 10, the number of layers of the film feed units is 20 and the diameter of the vertical reactor thoroughly mixed stream 2.5 times greater than the diameter of the vertical plug-flow reactor. A mixture of the oligomer and the melt of the modifying superconcentrate of polytetramethylene adipamide is subjected to an exchange reaction using an ester in the exchange reaction system to obtain an ethylene terephthalate / polytetramethylene adipamide copolymer and then delivered directly to the preliminary polycondensation system for the preliminary polycondensation reaction, the exchange reaction system has a temperature of 29 ° C ° C and a reaction time of 90 minutes

The pre-polycondensation system consists of a vertical first pre-condensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 295 ° C and the temperature of the reagent of the second pre-condensation reactor is 300 ° C. When the intrinsic viscosity of the prepolymer reaches 0.20 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation reactor is 300 ° C. When the intrinsic viscosity of the final polymer reaches 0.85 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a hydrophilic polyester fiber having a specific breaking strength of 3.8 CN / dtex, a tensile elongation of 42%, and a class 4.5 dye uniformity. The fiber dyeing results show that the molecular segment of the polytetramethylene adipamide modifier is uniformly distributed in the structure of the polyester molecules, so that the hydrophilic polyester is structurally uniform and its dyeing does not have chromatic aberration.

Embodiment 9

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2808 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 264 ° C, and the reaction temperature in the second esterification reactor is 267 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 5, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the second esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2340 kg / h.

The oligomer from the esterification system is cooled to 250 ° C using a multi-tube heat exchanger and enters the dynamic mixer together with the solution modified with polyethylene glycol from the flow injection device of the modifier solution, the solution of polyethylene glycol having a mass concentration of 90%, the injection temperature is 80 ° C, the injection speed 300 kg / h and a dynamic viscosity of 5 Pa⋅s, and the technological sequence of injection of a solution of polyethylene glycol is as follows: polyethylene glycol is added to p The reservoir for the preparation of a modifier solution having a mass concentration of ethylene glycol of 90%, after which the solution is sent to the reservoir for supplying the modifier solution due to the potential difference and the dosing pump of the modifier solution, is pumped into the supply pipe of the dynamic mixer through the modifier solution injector when measuring the flow rate and adjusting it in depending on the ratio of the oligomer flow rate obtained from the oligomer delivery dosing device.

The oligomer and the solution of the polyethylene glycol modifier are homogeneously mixed with a high-shear 2-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 230 ° C, the rotation speed of 3500 rpm, the ratio of length to vertical diameter a reactor with a fully mixed flow of the exchange reaction system is 2, the number of mixing paddle groups is 4, the ratio of the length to the diameter of the vertical reactor with a piston evym stream is 5, the number of layers of the film feed units is 10, and the diameter of the vertical reactor thoroughly mixed stream 1.5 times greater than the diameter of the vertical plug-flow reactor. The mixture of the oligomer and the polyethylene glycol modifier solution a is subjected to a transesterification reaction in an exchange reaction system to produce an ethylene terephthalate / polyethylene glycol copolymer and then delivered directly to the preliminary polycondensation system for preliminary polycondensation, the exchange reaction system having a reaction temperature of 250 ° C. and a reaction time of 45 minutes .

The preliminary polycondensation system consists of a vertical polycondensation reactor, and the reaction temperature in the preliminary polycondensation reactor is 275 ° C. When the intrinsic viscosity of the prepolymer reaches 0.30 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 280 ° C. When the intrinsic viscosity of the final polymer reaches 0.90 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a hydrophilic polyester fiber having a specific tensile load of 3.6 CN / dtex, a tensile elongation of 35% and a uniformity of class 4.5 dye. The fiber dyeing results show that the molecular segment of the polyethylene glycol modifier is uniformly distributed in the structure of the polyester molecules, so that the hydrophilic polyester is structurally uniform, and its dyeing does not have chromatic aberration.

Embodiment 10

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2902 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 260 ° C, and the reaction temperature in the second esterification reactor is 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 5, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the second esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2418 kg / h.

The oligomer from the esterification system is cooled to 255 ° C using a one-pipe heat exchanger and enters the dynamic mixer together with a flame-retardant solution modified with ethylene-2-carboxyethyl phenylphosphinate, from the flow-through injection of a modifier solution, and the fire-resistant solution of ethylene-2-carboxyethyl phenylphosphinate 50% , the injection temperature is 60 ° C, the injection speed is 490 kg / h and the dynamic viscosity is 1.5 Pa · s, and the technological sequence of injection of the ethylene-2-carboxy solution of phenylphosphinate is as follows: an esterification solution of 2-carboxyethyl phenylphosphinate with an degree of esterification of 85% is added to the reservoir for preparing a modifier solution having a mass concentration of ethylene glycol of 50%, after which the solution is sent to the reservoir for supplying the modifier solution due to the potential difference and the metering pump pumps the modifier solution into the dynamic mixer feed pipe through the injector of the modifier solution when measuring the flow rate and its regulation and depending on the ratio of the oligomer flow rate obtained from the oligomer delivery dosing device.

The oligomer and ethylene-2-carboxyethyl phenylphosphinate modifier solution are homogeneously mixed with a 5-step high shear dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 230 ° C, the rotation speed being 50 rpm, the ratio length to diameter of a vertical reactor with a fully mixed flow of the exchange reaction system is 0.5, the number of mixing paddle groups is 2, the ratio of length to diameter is vertical a plug-flow reactor is 2, the number of layers of the film feed units is 4, and the diameter of the vertical reactor thoroughly mixed stream into 1.05 times the diameter of a vertical reactor with plug flow. A mixture of an oligomer and an ethylene-2-carboxyethyl phenylphosphinate modifier solution is subjected to transesterification in an exchange reaction system to obtain an ethylene terephthalate / ethylene-2-carboxyethyl phenylphosphinate copolymer, after which the oligomer pump is delivered directly to the preliminary polycondensation system to carry out the preliminary polycondensation reaction reaction 255 ° C and a reaction time of 10 minutes

The pre-polycondensation system consists of a vertical first pre-polycondensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 265 ° C and the temperature of the reagent of the second pre-condensation reactor is 270 ° C. When the intrinsic viscosity of the prepolymer reaches 0.10 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor and a horizontal liquid phase tackifier, the temperature of the final polycondensation reaction in the reactor is 275 ° C, and the temperature of the liquid tack increase in the reactor is 280 ° C. When the intrinsic viscosity of the adhesive final polymer reaches 0.75 dl / g, the modified polyester melt is delivered through a pipe directly to the spinning section for spinning to produce the modified polyester fiber.

The fiber is a flame retardant polyester fiber having a specific tensile load of 2.8 CN / dtex, a tensile elongation of 25%, and a class 4.5 dye uniformity. Fiber dyeing results show that the molecular segment of the ethylene-2-carboxyethylphenylphosphinate modifier is uniformly distributed in the structure of the polyester molecules, so that the high modulus polyester is structurally uniform and does not have chromatic aberration.

Embodiment 11

The suspension prepared from terephthalic acid and butanediol is continuously and uniformly delivered at a flow rate of 2496 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor with structurally adjacent chambers for the purpose of carrying out the esterification reaction, the reaction temperature in the first the esterification reactor is 230 ° C., and the reaction temperature in the second esterification reactor is 240 ° C. An esterification catalyst tetrabutyl titanate solution at a mass concentration of 3% is continuously and uniformly introduced into the first esterification reactor at a flow rate of 41.7 kg / h; and a polycondensation catalyst, i.e. a composite catalytic solution of tetrabutyl titanate and antimony acetate at a mass concentration of 5%, is continuously and uniformly introduced into the third chamber of the second esterification reactor at a flow rate of 41.7 kg / h. When the polymerization degree of the esterified butylene terephthalate oligomer reaches 1, the esterified butylene terephthalate oligomer is continuously and stably removed from the esterification reactor by an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2080 kg / h

The oligomer from the esterification system is cooled to 180 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polybutylene succinate from the in-line injection device of the modifying superconcentrate, and the melt of the polybutylene succinate superconcentrate during injection has a temperature of 160 ° C and the injection speed kg / h, and the dynamic viscosity is 800 Pa⋅s, with the technological sequence of injection of polybutylene succinate superconcentrate vgl dit follows: masterbatch of polybutylene succinate is dried by a dryer system modifier masterbatch melted screw ekstruderomi injected into the feed tube dynamic mixer directly metering pump melt modifier masterbatch when measuring the flow velocity and its regulation depending on the relation with the oligomer flow rate exiting the oligomeric dispenser.

The oligomer and the melt of the modified modifier polybutylene succinate superconcentrate are homogeneously mixed with a 5-step high shear dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 180 ° C, the rotation speed is 3000 rpm, the length to the diameter of the vertical reactor with a fully mixed stream of the exchange reaction system is 2, the number of mixing paddle groups is 4, the length ratio the diameter of the vertical reactor with a piston flow is 10, the number of layers of the film supply units is 30, and the diameter of a vertical reactor with a fully mixed flow is 2 times the diameter of a vertical reactor with a piston flow. The mixture of the oligomer and the melt of the modifying superconcentrate of polybutylene succinate is subjected to a transesterification reaction in an exchange reaction system to produce a butylene terephthalate / polybutylene succinate copolymer, and then it is delivered directly to the preliminary polycondensation system for the preliminary polycondensation, the exchange reaction system having a reaction temperature of 180 ° C. min

The preliminary polycondensation system consists of a vertical polycondensation reactor, and the reaction temperature in the preliminary polycondensation reactor is 200 ° C. When the intrinsic viscosity of the prepolymer reaches 0.50 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 200 ° C. When the intrinsic viscosity of the final polymer reaches 1.20 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a biodegradable polyester fiber having a specific tensile load of 3.0 CN / dtex, an elongation of 45% and uniformity of the dye class 4. The results of fiber dyeing show that the molecular segment of the polybutylene succinate modifier is uniformly distributed in the structure of the polyester molecules, so the biodegradable complex the polyester is structurally uniform, and its dyeing does not have chromatic aberration.

Embodiment 12

The suspension prepared from terephthalic acid and butanediol is continuously and uniformly delivered at a flow rate of 2328 kg / h to the esterification reaction system consisting of a vertical esterification reactor in order to carry out the esterification reaction at a reaction temperature of 230 ° C. A catalytic solution of tetraisopropyl titanate at a mass concentration of 10% is continuously and uniformly injected into the esterification reactor at a flow rate of 17.5 kg / h. When the polymerization degree of the esterified butylene terephthalate oligomer reaches 2, the esterified butylene terephthalate oligomer is continuously and stably removed from the esterification reactor by an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 1820 kg / h

The oligomer from the esterification system is cooled to 200 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polybutylene adipate from the in-line injection device of the modifying superconcentrate, and the melt of the polybutylene adipate superconcentrate during injection has a temperature of 200 ° C, the injection speed is 750 ° C kg / h, and the dynamic viscosity is 5 Pa⋅s, and the technological sequence of injection of polybutylene adipate superconcentrate looks like In the following way: the polybutylene adipate superconcentrate is dried using a modifying superconcentrate drying system, melted with a screw extruder and injected directly into the dynamic mixer feed tube with the melt pump of the modifying superconcentrate when measuring the flow rate and adjusting it depending on the ratio with the flow rate of the oligomer leaving the oligomeric dispenser.

The oligomer and the melt of the modifying superconcentrate of the polybutylene adipate modifier are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 200 ° C, the rotation speed is 4000 rpm, the length to the diameter of the vertical reactor with a fully mixed flow of the exchange reaction system is 3, the number of mixing paddle groups is 5, the ratio of length to diameter etru vertical plug-flow reactor is 15, the number of layers of the film feed units is 40, and the diameter of a vertical reactor with fully kneaded flow 5 times greater than the diameter of the vertical plug-flow reactor. The mixture of the oligomer and the melt of the modifying superconcentrate of polybutylene adipate is subjected to transesterification in the exchange reaction system to produce a butylene terephthalate / polybutylene adipate copolymer and then delivered directly to the pre-polycondensation system for pre-polycondensation with the oligomer pump, and the exchange reaction system has a reaction temperature of 200 ° C and a reaction time min

The preliminary polycondensation system consists of a vertical polycondensation reactor, and the reaction temperature in the preliminary polycondensation reactor is 210 ° C. When the intrinsic viscosity of the prepolymer reaches 0.45 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 220 ° C. When the intrinsic viscosity of the final polymer reaches 1.50 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a biodegradable polyester fiber having a specific tensile load of 2.7 CN / dtex, a 50% elongation at break and uniformity of class 4.5 dye. The fiber dyeing results show that the molecular segment of the polybutylene adipate modifier is uniformly distributed in the structure of the polyester molecules, so that the biodegradable polyester is structurally uniform and its dyeing does not have chromatic aberration. Embodiment 13

The suspension prepared from terephthalic acid and butanediol is continuously and uniformly delivered at a flow rate of 2993 kg / h to the esterification reaction system consisting of a vertical esterification reactor to carry out the esterification reaction at a reaction temperature of 230 ° C. A catalytic solution of tetraisopropyl titanate at a mass concentration of 10% is continuously and uniformly injected into the esterification reactor at a flow rate of 17.5 kg / h. When the polymerization degree of the esterified butylene terephthalate oligomer reaches 3, the esterified butylene terephthalate oligomer is continuously and stably removed from the esterification reactor by an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 1820 kg / h

The oligomer from the esterification system is cooled to 200 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polyethylene adipate from the in-line injection device of the modifying superconcentrate, and the molten superconcentrate of polyethylene adipate during injection has a temperature of 180 ° C, the injection speed is 250 ° C kg / h, and the dynamic viscosity is 60 Pa⋅s, and the technological sequence of injection of polyethylene adipate superconcentrate looks like manner: masterbatch polyethylene adipate is dried by a dryer system modifier masterbatch melted screw extruder and injected into the feed tube dynamic mixer directly metering pump melt modifier masterbatch when measuring the flow velocity and its regulation depending on the relation with the oligomer flow rate exiting the oligomeric dispenser.

The oligomer and melt of the modifying superconcentrate of the polybutylene adipate modifier are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 200 ° C, the rotation speed is 2000 rpm, the length to the diameter of the vertical reactor with a fully mixed flow of the exchange reaction system is 2, the number of mixing paddle groups is 4, the ratio of length to diameter etru vertical plug-flow reactor is 10, the number of layers of the film feed units equal to 25, and the diameter of the vertical reactor thoroughly mixed stream 3.5 times greater than the diameter of the vertical plug-flow reactor. The mixture of oligomer and melt of the modifying superconcentrate of polyethylene adipate is subjected to transesterification in the exchange reaction system for the production of butylene terephthalate / ethylene adipate oligomer and then delivered directly to the pre-polycondensation system for pre-polycondensation, the exchange reaction system having a reaction temperature of 220 ° C and a reaction time of 75 min

The preliminary polycondensation system consists of a vertical polycondensation reactor, wherein the reaction temperature in the preliminary polycondensation reactor is 230 ° C. When the intrinsic viscosity of the prepolymer reaches 0.30 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 240 ° C. When the intrinsic viscosity of the final polymer reaches 1.30 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a biodegradable polyester fiber having a specific tensile load of 3.4 CN / dtex, a tensile elongation of 28%, and a class 5 dye uniformity. The fiber dyeing results show that the molecular segment of the polyethylene adipate modifier is uniformly distributed in the structure of the polyester molecules so that the biodegradable complex the polyester is structurally uniform, and its dyeing does not have chromatic aberration.

Embodiment 14

The suspension prepared from terephthalic acid and propanediol is continuously and uniformly delivered at a flow rate of 3026 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor with structurally adjacent chambers in order to carry out the esterification reaction, the reaction temperature in the first the esterification reactor is 225 ° C., and the reaction temperature in the second esterification reactor is 235 ° C. The esterification catalytic solution of titanium glycolate at a mass concentration of 3% is continuously and uniformly introduced into the first esterification reactor at a flow rate of 41.6 kg / h; and a polycondensation catalyst, i.e. a catalytic antimony ethylene glycolate solution, at a mass concentration of 3%, is continuously and uniformly introduced into the third chamber of the second esterification reactor at a flow rate of 41.6 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the esterified ethylene terephthalate oligomer is continuously and stably removed from the second esterification reactor by an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2522 kg / h

The oligomer from the esterification system is cooled to 220 ° C using a Sulzer type heat exchanger and enters the dynamic mixer together with a solution modified with sodium 5-sulfo-bis (hydroxypropyl) -isophthalate, and a flow injection device of the modifier solution. The mass concentration of the sodium-5-sulfo-bis (hydroxypropyl) -isophthalate solution is 20%, the injection temperature is 110 ° C, the injection speed is 482 kg / h, and the dynamic viscosity is 0.05 Pa⋅s, and the technological sequence of the solution injection sodium 5-sulfo-bis (hydroxypropyl) -isophthalate is as follows: an esterification solution of sodium-5-sulfo-bis (hydroxypropyl) -isophthalate is added to the tank for preparing a modifier solution to form a solution having a mass concentration of 2 0% with propylene glycol, and then the solution is transferred to the reservoir for supplying the modifier solution, due to the potential difference, the modifier solution is injected into the feed pipe of the dynamic mixer through the modifier solution feed pipe with the modifier solution injector with flow rate measurement and its regulation depending on the ratio with the oligomer flow rate output from an oligomer delivery dosing device.

The oligomer and the sodium-5-sulfo-bis (hydroxypropyl) -isophthalate modifier solution are homogeneously mixed with a high-shear 1-stage dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 230 ° С, rotation speed is 300 rpm, the ratio of length to diameter of a vertical reactor with a fully mixed flow of the exchange reaction system is 0.8, the number of mixing paddle groups is 2, the ratio of length to diameter have vertical plug-flow reactor is 4, the number of layers of the film feed units is 10, and the diameter of a vertical reactor with fully kneaded twice the flow diameter vertical reactor with plug flow. A mixture of the oligomer and the sodium-5-sulfo-bis (hydroxypropyl) -isophthalate modifier solution is subjected to transesterification in an exchange reaction system to obtain an ethylene terephthalate / sodium-5-sulfo-bis (hydroxypropyl) -isophthalate copolymer, after which the oligomer pump is delivered directly to the system preliminary polycondensation for conducting the preliminary polycondensation reaction, wherein the exchange reaction system has a reaction temperature of 235 ° C. and a reaction time of 30 minutes.

The preliminary polycondensation system consists of a vertical polycondensation reactor, and the reaction temperature in the preliminary polycondensation reactor is 250 ° C. When the intrinsic viscosity of the prepolymer reaches 0.35 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 260 ° C. When the intrinsic viscosity of the final polymer reaches 1.05 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a dyeable polyester fiber with a cationic dye, having a specific tensile load of 2.8 CN / dtex, a tensile elongation of 38%, and a class 5 dye uniformity. The fiber dyeing results show that the sodium-5-sulfo-bis (hydroxypropyl) modifier segment is β-isophthalate is homogeneously distributed in the structure of polyester molecules, so that the colorant to be coated with a cationic dye is structurally homogeneous and its coloring does not have chromatic aberration.

Embodiment 15

A suspension prepared from terephthalic acid and cyclohexanedimethanol is continuously and uniformly delivered at a flow rate of 2496 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 270 ° C, and the reaction temperature in the second esterification reactor is 280 ° C. The esterification catalytic solution of antimony trioxide ethylene glycolate at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 25 kg / h. When the polymerization degree of the esterified cyclohexane dimethanol terephthalate oligomer reaches 6, the esterified cyclohexane dimethanol terephthalate oligomer is continuously and stably removed from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2080 kg / h

The oligomer from the esterification system is cooled to 275 ° C using a single-tube heat exchanger and enters the dynamic mixer together with the melt of the modifying superconcentrate of polyethylene terephthalate from the in-line injection device of the modifying superconcentrate, and the molten superconcentrate of polyethylene terephthalate during injection has a temperature of 275 ° C, the injection speed is 500 kg / h , and the dynamic viscosity is 300 Pa⋅s, and the technological sequence of injection of superconcentrate of polyethylene terephthalate vyg It looks as follows: a polyethylene terephthalate superconcentrate is dried using a modifying superconcentrate drying system, melted with a screw extruder and injected into the dynamic mixer feed pipe directly with a melt modifying superconcentrate metering pump when measuring the flow rate and adjusting it depending on the ratio with the flow rate of the oligomer leaving the oligomeric doser .

The oligomer and melt of the modifier polybutylene terephthalate superconcentrate melt are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 275 ° C, the rotation speed being 2500 rpm, the length to diameter ratio a vertical reactor with a fully mixed flow of the exchange reaction system is 3, the number of mixing paddle groups is 5, the ratio of length to diameter is tikalnogo plug-flow reactor is 8, the number of layers of the film feed units equal to 25, and the diameter of the vertical reactor thoroughly mixed stream 3 times larger than the diameter of the vertical plug-flow reactor. The mixture of the oligomer and the melt of the modifying superconcentrate of polyethylene terephthalate is subjected to transesterification in the exchange reaction system to produce the cyclohexane dimethanol terephthalate / ethylene terephthalate oligomer and then the oligomer pump is delivered directly to the preliminary polycondensation system for preliminary polycondensation, and the exchange reaction system has a reaction time of 90 ° C and a reaction temperature of 275 ° C .

The pre-polycondensation system consists of a vertical first pre-condensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 280 ° C and the temperature of the reagent of the second pre-condensation reactor is 285 ° C. When the intrinsic viscosity of the prepolymer reaches 0.25 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 290 ° C. When the intrinsic viscosity of the final polymer reaches 0.67 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a highly shrinkable polyester fiber having a specific tensile load of 3.2 CN / dtex, a 45% elongation and uniformity of class 4 dye. The fiber dyeing results show that the molecular segment of the polyethylene terephthalate modifier is uniformly distributed in the structure of the polyester molecules, so that polyester with a high degree is structurally homogeneous, and its dyeing has no chromatic aberration. Option exercise 16

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2808 kg / h to an esterification system consisting of a vertical first esterification reactor and a horizontal second esterification reactor to carry out the esterification reaction, the reaction temperature in the first esterification reactor being 260 ° C, and the reaction temperature in the second esterification reactor is 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the second esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 8, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the second esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2340 kg / h

The oligomer from the esterification system is cooled to 230 ° C using a Sulzer type heat exchanger, after which it enters the dynamic mixer together with the sodium-5-sulfo-bis (hydroxyethyl) -isophthalate modifier from the flow injection device of the modifier solution and the modifying superconcentrate of polybutylene succinate from a flow injection device of a modifying superconcentrate, wherein the sodium 5-sulfo-bis (hydroxyethyl) -isophthalate solution has a mass concentration of 40%, an injection temperature of 80 ° C., an injection rate of 348 kg / h and din ical viscosity of 0.6 Pa.s and the melt masterbatch polybutylene succinate has an injection temperature of 160 ° C, an injection speed of 250 kg / h and a dynamic viscosity of 800 Pa · s. The technological sequence of injection of a solution of sodium 5-sulfo-bis (hydroxyethyl) -isophthalate is as follows: an esterification solution of sodium-5-sulfo-bis (hydroxyethyl) -isophthalate is added to the tank for preparing a modifier solution in order to prepare a solution having a mass concentration of 40 % ethylene glycol, after which the solution is transferred to the modifier solution supply tank due to the potential difference and introduced into the supply pipe of the dynamic mixer by the metering solution pump dosing modifier and through the injector of the injection of the modifier solution with the measurement of the flow rate and its regulation depending on the ratio of the flow rate of the oligomer leaving the oligomer delivery dispensing device; and the technological sequence of injection of the melt of the modifying superconcentrate of polybutylene succinate is as follows: the modifying superconcentrate of polybutylene succinate is dried by the drying system of the modifying superconcentrate, is melted by a screw extruder and injected directly into the dynamic mixer feed pipe with a metering pump to supply the melt of the modifying superconcentrate with the measurement of the flow rate as a function of the flow rate the flow of oligomer derived from y troystva dosing delivery of oligomers.

The oligomer and the solution of sodium 5-sulfo-bis (hydroxyethyl) -isophthalate and the superconcentrate modifying polybutylene succinate are homogeneously mixed with a high-shear 3-stage dynamic mixer and then introduced into the exchange reaction system to carry out the exchange reaction, the temperature of the dynamic mixer being 230 ° С , the rotation speed is 1500 rpm, the ratio of length to diameter of a vertical reactor with a fully mixed flow of the exchange reaction system is 1, the number of mixing blades x groups is 2, the ratio of length to diameter of a vertical reactor with a piston flow is 10, the number of layers of the film supply units is 20, and the diameter of a vertical reactor with a fully mixed flow is 1.2 times the diameter of a vertical reactor with a piston flow. A mixture of an oligomer and a solution of sodium 5-sulfo-bis (hydroxyethyl) -isophthalate and a modifying superconcentrate of polybutylene succinate is subjected to transesterification in the exchange reaction system to obtain the ternary ethylene terephthalate / sodium 5-sulfo-bis (hydroxyethyl) isophthalate oligomer, followed by an oligomer the pump is delivered directly to the preliminary polycondensation system for conducting the preliminary polycondensation reaction, the exchange reaction system having a reaction temperature of 235 ° C. and a reaction time of 60 minutes.

The pre-condensation system consists of a vertical first pre-condensation reactor and a horizontal second pre-condensation reactor, wherein the temperature of the reagent of the first pre-condensation reactor is 255 ° C. and the temperature of the reagent of the second pre-condensation reactor is 265 ° C. When the intrinsic viscosity of the prepolymer reaches 0.20 dl / g, the prepolymer is continuously and continuously removed from the second pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 275 ° C. When the intrinsic viscosity of the final polymer reaches 0.62 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a polyester fiber dyed with a cationic dye at normal pressure: it has a specific tensile load of 3.4 CN / dtex, a tensile elongation of 35% and uniformity of class 5 dye. The fiber dyeing results show that the segment of the sodium 5-sulfo bis modifier (hydroxyethyl) isophthalate and the polybutylene succinate segment are homogeneously distributed in the structure of the polyester molecules, so that the cation dye-dyed polyester is structurally homogeneous and does not have chromatic aberration .

Embodiment 17

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2964 kg / h to the esterification reaction system consisting of a vertical esterification reactor in order to carry out the esterification reaction at a reaction temperature of 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2470 kg / h

The oligomer from the esterification reaction system is cooled to 250 ° C using a Sulzer type heat exchanger, after which it enters the dynamic mixer together with the melt of the modifying superconcentrate of polycaprolactam from the flow injection device of the modifying superconcentrate, and the melt of the polycaprolactam superconcentrate has a temperature of 250 ° C during injection, the injection flow rate is 125 kg / h, and the dynamic viscosity is 180 Pa · s, and the process sequence for the injection of superconcentrate polik prolactam is as follows: the polycaprolactam superconcentrate is dried by the drying system of the modifying superconcentrate, melted by a screw extruder and injected into the feed pipe of the dynamic mixer directly through the dosing pump of the melt of the modifying superconcentrate when measuring the flow rate and adjusting it depending on the ratio with the flow rate of the oligomer exiting the dosing device oligomer delivery.

The oligomer and melt of the polycaprolactone modifier superconcentrate are homogeneously mixed with a 5-stage high shear dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 250 ° C, the rotation speed is 3000 rpm, the length to diameter ratio a vertical reactor with a fully mixed flow of the exchange reaction system is 0.4, the number of mixing paddle groups is 1, the ratio of the length to the diameter of the vertical nogo plug-flow reactor is 30, the number of layers of the film feed units is 60 and the diameter of a vertical reactor with a fully-mixed flow is twice the diameter of a vertical reactor with plug flow. The mixture of the oligomer and the melt of the modifying polycaprolactam superconcentrate is subjected to an exchange reaction using an ester in the exchange reaction system to obtain an ethylene terephthalate / caprolactam copolymer and then delivered directly to the preliminary polycondensation system for the preliminary polycondensation reaction, the exchange reaction system having a reaction temperature of 260 ° C. and a reaction time of 90 minutes

The preliminary polycondensation system consists of a vertical polycondensation reactor, the reaction temperature in the preliminary polycondensation reactor is 270 ° C. When the intrinsic viscosity of the prepolymer reaches 0.30 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation boiler is 280 ° С. When the intrinsic viscosity of the final polymer reaches 0.80 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a hydrophilic polyester fiber having a specific tensile load of 2.7 CN / dtex, an elongation of 23% and a uniformity of dye class 4.0. The fiber dyeing results show that the molecular segment of the polycaprolactam modifier is evenly distributed in the structure of the polyester molecules, so that the hydrophilic polyester is structurally uniform and its dyeing does not have chromatic aberration.

Embodiment 18

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2964 kg / h to the esterification reaction system consisting of a vertical esterification reactor in order to carry out the esterification reaction at a reaction temperature of 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2470 kg / h

The oligomer from the esterification reaction system is cooled to 305 ° C using a Sulzer type heat exchanger, after which it enters the dynamic mixer together with the melt of the modifying superconcentrate of polycaprolactam from the flow injection device of the modifying superconcentrate, and the melt of the polycaprolactam superconcentrate has a temperature of 250 ° C during injection the injection flow rate is 125 kg / h, and the dynamic viscosity is 1100 Pa · s, and the process sequence for the injection of superconcentrate polik Aprolactam is as follows: the polycaprolactam superconcentrate is dried by the drying system of the modifying superconcentrate, melted by a screw extruder and injected into the feed tube of the dynamic mixer directly through the dosing pump of the melt of the modifying superconcentrate when measuring the flow rate and its regulation depending on the ratio with the flow rate of the oligomer exiting the dosing device oligomer delivery.

The oligomer and melt of the polycaprolactone modifier superconcentrate are homogeneously mixed with a 5-stage high-shear dynamic mixer and then introduced into the exchange reaction system to perform the exchange reaction, the temperature of the dynamic mixer being 250 ° C, the rotation speed is 3000 rpm, the length to diameter ratio vertical reactor with a fully mixed flow of the exchange reaction system is 0.4, the number of mixing paddle groups is 1, the ratio of the length to the diameter of the vertical nogo plug-flow reactor is 1.8, the number of layers of the film feed units is 3, and the diameter of a vertical reactor with a fully-mixed flow is twice the diameter of a vertical reactor with plug flow. The mixture of the oligomer and the melt of the polycaprolactam modifying superconcentrate is subjected to an exchange reaction using an ester in the exchange reaction system to obtain an ethylene terephthalate / caprolactam copolymer and then delivered directly to the preliminary polycondensation system for the preliminary polycondensation reaction, the exchange reaction system having a reaction temperature of 305 ° C. and a reaction time of 8 minutes

The preliminary polycondensation system consists of a vertical polycondensation reactor, the reaction temperature in the preliminary polycondensation reactor is 270 ° C. When the intrinsic viscosity of the prepolymer reaches 0.09 dl / g, the prepolymer is continuously and continuously removed from the pre-condensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation boiler is 280 ° С. When the intrinsic viscosity of the final polymer reaches 0.48 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a hydrophilic polyester fiber having a specific tensile load of 2.5 CN / dtex, a tensile elongation of 20%, and a class 4.0 dye uniformity. The fiber dyeing results show that the molecular segment of the polycaprolactam modifier is evenly distributed in the structure of the polyester molecules, so that the hydrophilic polyester is structurally uniform and its dyeing does not have chromatic aberration.

Comparative embodiment 1

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2964 kg / h to the esterification reaction system consisting of a vertical esterification reactor in order to carry out the esterification reaction at a reaction temperature of 265 ° C. The catalytic antimony ethylene glycolate solution at a mass concentration of 3% is continuously and uniformly injected into the esterification reactor at a flow rate of 35.9 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2470 kg / h

The oligomer from the esterification system enters the preliminary polycondensation system for conducting the preliminary condensation reaction together with the melt of the modifying superconcentrate of polycaprolactam from the flow injection device of the modifying superconcentrate, the melt of the polycaprolactam superconcentrate having a temperature of 250 ° C during injection, the injection flow rate is 125 kg / h, and the dynamic viscosity is 180 Pa⋅s, and the process sequence for the injection of polycaprolactam superconcentrate is it looks as follows: polycaprolactam superconcentrate is dried by the drying system of the modifying superconcentrate, melted by a screw extruder and injected into the oligomeric tube directly through the dosing pump of the melt of the modifying superconcentrate.

The preliminary polycondensation system consists of a vertical polycondensation reactor, the reaction temperature in the preliminary polycondensation reactor is 270 ° C. When the intrinsic viscosity of the prepolymer reaches 0.30 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, the reaction temperature in the final polycondensation boiler is 280 ° С. When the intrinsic viscosity of the final polymer reaches 0.80 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a hydrophilic polyester fiber having a specific tensile load of 2.2 CN / dtex, a tensile elongation of 15%, and a class 2 dye uniformity. The fiber dyeing results show that the molecular segment of the polycaprolactam modifier is unevenly distributed in the structure of the polyester molecules, so that the hydrophilic complex the polyester is not structurally homogeneous enough, and its dyeing has chromatic aberration.

Comparative embodiment 2

The suspension prepared from terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2964 kg / h to the esterification reaction system consisting of a vertical esterification reactor to carry out the esterification reaction at a reaction temperature of 261 ° C. A solution of catalytic antimony acetate at a mass concentration of 3.5% is continuously and uniformly injected into the esterification reactor at a flow rate of 41.5 kg / h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the esterified ethylene terephthalate oligomer is continuously and stably extracted from the esterification reactor through an oligomer delivery metering device consisting of an oligomer pump and an oligomer flow meter at a flow rate of 2246 kg / h

The oligomer from the esterification system enters the dynamic mixer together with the solution modified with sodium 5-sulfo-bis (hydroxyethyl) -isophthalate, and the flow injection device of the modifier solution. The mass concentration of the sodium-5-sulfo-bis (hydroxyethyl) -isophthalate solution is 25%, the injection temperature is 90 ° C, the injection speed is 186 kg / h, and the dynamic viscosity is 0.1 Pa⋅s, and the technological sequence of the solution injection sodium 5-sulfo-bis (hydroxyethyl) -isophthalate is as follows: The esterification solution of sodium-5-sulfo-bis (hydroxyethyl) -isophthalate is added to the reservoir for preparing a modifier solution to create a solution having a mass concentration of 25% ethylene glyco After that, the solution is delivered to the modifier solution supply tank due to the potential difference and the modifier solution dosing pump is introduced into the supply pipe of the dynamic mixer through the modifier solution injector with flow rate control and its regulation depending on the ratio with the oligomer flow rate output from the dosing device oligomer delivery.

The oligomer and sodium-5-sulfo-bis (hydroxyethyl) -isophthalate modifier are homogeneously mixed with a high-shear 3-stage dynamic mixer, after which they are introduced into the preliminary polycondensation system for the preliminary polycondensation reaction, and the temperature of the dynamic mixer is 230 ° C, and rotation speed 1000 rpm; moreover, the preliminary polycondensation system consists of a vertical reactor for preliminary polycondensation, and the temperature of the reagent in the preliminary polycondensation reactor is 260 ° C. When the intrinsic viscosity of the prepolymer reaches 0.15 dl / g, the prepolymer is continuously and continuously removed from the pre-polycondensation reactor by the prepolymer pump and delivered to the final polycondensation system to conduct the final polycondensation reaction. The final polycondensation system consists of a horizontal final polycondensation reactor, wherein the reaction temperature in the final polycondensation reactor is 275 ° C. When the intrinsic viscosity of the final polymer reaches 0.50 dl / g, the modified polyester melt is delivered directly to the spinning section through the spinning pipe to produce the modified polyester fiber.

The fiber is a polyester fiber dyed with a cationic dye, having a specific tensile load of 2.3 CN / dtex, an elongation at break of 18% and uniformity of the dye of class 3.5. The fiber dyeing results show that the sodium 5-sulfo-bis (hydroxyethyl) -isophthalate modifier segment is not homogeneously distributed in the structure of the polyester molecules, so that the dyeable polyester with a cationic dye is structurally not homogeneous and its dyeing has chromatic aberration.

Modified continuous spinning polyester fibers of Embodiments 1-16 and Comparative Embodiments 1 and 2, as mentioned above, are tested for their characteristics, namely, the following characteristics are checked: specific breaking load (CN / dtex), test method : according to GB / T 14344-2008; elongation at break (%), test method: according to GB / T 14344-2008; and dye uniformity, test method: according to GB / T 6508-2001. The test results are shown in table 1.

Based on the data presented in table 1, the continuous continuous modified polyester fiber obtained by the method for producing the modified polyester fiber in accordance with the present invention has a specific tensile load of 2.5 CN / dtex to 6.0 CN / dtex, elongation from 20% up to 50% and uniformity of dye of class 4-5, and in terms of specific breaking load and elongation at break at break, the fiber can not only meet the requirements for the subsequent twisting stage, but also has a higher dye uniformity than the modified modified polyester fiber products obtained in the prior art, which indicates that the modified polyester fiber obtained by the modified polyester fiber production method in accordance with the present invention has higher structural uniformity.

To further illustrate the advantageous results of the modified polyester production method in accordance with the present invention, the thermal properties of the modified polyester fibers obtained in Embodiment 1 and Comparative Embodiment 1 of the present invention are compared by analysis using differential scanning calorimetry. Test method: first, a Pyris 1 differential scanning calorimeter from Perkin Elmer is used to quickly heat samples to 280 ° C, the temperature is maintained for 5 minutes to completely eliminate the history of temperature increase, then the samples are quenched in liquid nitrogen, after which the samples are heated from 30 up to 280 ° C at a rate of 20 ° C / min, in FIG. 4 shows the DSC scan curves of the modified polyesters, wherein chart a is a graph of the temperature increase of the DSC modified polyester obtained in the first embodiment, and diagram b is a graph of the temperature increase of the DSC modified polyester obtained in comparative embodiment 1.

As can be seen in FIG. 4, there is only one melting peak in the DCS temperature graph of the modified polyester obtained in Embodiment 1, with its maximum value being 233.3 ° C., while the DCS temperature graph of the modified polyester obtained in comparative embodiment 1, two melting peaks appear, with peak values being 203.6 ° C and 248.9 ° C, respectively, which indicates that the segment of the polycaprolactam modifier in the modified polyester prepared in the embodiment is 1, is homogeneously distributed in the structure of the polyester molecule, thereby forming a structurally homogeneous block copolymer of polyester-polycaprolactam. The modifier polycaprolactam in the modified polyester obtained in comparative embodiment 1 is present as a mixture or as a long segment embedded in the molecular chain of the polyester, which leads to lower structural uniformity of the modified polyester.

All source material compositions, esterification reaction conditions and polycondensation reaction conditions used in the preparation of the modified polyesters in Embodiment 1 and comparative embodiment 1 of the present invention are the same, the difference between the two production methods is that during the production of the modified polyester in Embodiment 1 The mixing procedure by a dynamic mixer and the exchange reaction procedure are introduced. An effective dispersion of the polycaprolactam modifier in the polyester oligomer is achieved using a dynamic mixer mixing procedure, so that the subsequent exchange reaction between the polycaprolactam modifier and the polyester oligomer is close to a homogeneous reaction; and the exchange reaction procedure allows the introduction of the polycaprolactam modifier into the base of the polyester oligomer molecule through the exchange reaction, thereby obtaining a structurally homogeneous oligomer of polyether polycaprolactam, thereby ensuring structural homogeneity of the final polycondensation product, i.e., the modified polyester. In addition, it can also be seen from Table 1 that the specific tensile load, elongation at break, and uniformity of the dye of the modified polyester fiber obtained in the first embodiment of the present invention significantly exceed the specific tensile load of the modified polyester fibers obtained in comparative embodiment 1.

In order to specifically illustrate the beneficial effects of the exchange reaction procedure in the modified polyester production method of the present invention, an analysis was performed to compare the properties of the modified polyester fibers obtained in Embodiment 2 and Comparative Embodiment 2 of the present invention. All compositions of the starting material, the conditions of the esterification reaction, the conditions of the polycondensation reaction and the conditions of dynamic mixing used to obtain the modified polyesters in embodiment 2 and comparative embodiment 2 of the present invention are the same, the difference between the two production methods is that during the production of the modified polyester in option 2, the exchange reaction procedure is introduced. During the exchange reaction procedure, a uniform distribution of the sodium 5-sulfo-bis (hydroxyethyl) -isophthalate modifier in the structure of the polyester molecule is achieved, and the problem of the uneven distribution of sodium-5-sulfo-bis (hydroxyethyl) -isophthalate, characteristic of the prior art methods, is solved in the structure of the polyester molecule due to its self-polymerization. Table 1 also shows that the specific tensile load, elongation at break and uniformity of the dye of the modified polyester fiber obtained in Embodiment 2 of the present invention significantly exceed the specific tensile load of the modified polyester fibers obtained in Comparative Option 2.

Those options described above are simply preferred embodiments of the present invention and are not intended to limit the present invention, and for a person skilled in the art, the present invention may have various changes and modifications. Any changes, equivalent replacements, improvements, and the like, in accordance with the spirit and principles of the present invention are intended to be included within the scope of the present invention.

Claims (38)

1. The system of metabolic reactions, containing: a fully mixed flow vertical reactor (2) comprising a first material inlet (1) and a material outlet; a vertical piston flow reactor (7) comprising a second material inlet and a second material outlet (10); moreover, a vertical reactor (2) with a completely mixed flow is provided on the upper wall of the vertical reactor (7) with a piston flow and the first material outlet is connected to the second material inlet. 2. The exchange reaction system according to claim 1, in which the lower wall of the vertical reactor (2) with a fully mixed stream is at least partially common with the upper wall of the vertical reactor (7) with a piston flow in order to form a common wall of the reactor, and the first material outlet and the second material inlet overlap and are located on the common wall of the reactor. 3. The exchange reaction system according to claim 2, in which the common wall of the reactor has a structure in which the middle part is immersed downward relative to the vertical reactor (2) with a completely mixed stream. 4. The exchange reaction system according to claim 1, in which the vertical reactor (2) with a fully mixed flow and the vertical reactor (7) with a piston flow are coaxial, and preferably, the first material outlet and the second material inlet overlap and located on the axis of the vertical reactor (2) with a fully mixed stream and the vertical reactor (7) with a piston stream. 5. The exchange reaction system according to claim 1, in which the vertical reactor (2) with a fully mixed stream has a length to diameter ratio of 0.5 to 3, the vertical reactor (7) with a piston stream has a length to diameter ratio of 2 to 20 and the diameter of the vertical reactor (2) with a fully mixed flow is larger than that of a vertical reactor (7) with a piston flow; and, more preferably, the diameter of the vertical reactor (2) with a fully mixed stream is from 1.05 to 5 diameters of the vertical reactor (7) with a piston flow. 6. The exchange reaction system according to claim 1, wherein the exchange reaction system further comprises a cascade control system for the liquid level, comprising: a liquid level sensor used to determine information about the liquid level inside the vertical reactor (2) with a completely mixed flow and send a signal about the liquid level in accordance with the information about the liquid level; as well as an electric control valve located on the pipeline that connects the first outlet for the material of the vertical reactor (2) with a fully mixed flow and the second inlet for the material of the vertical reactor (7) with a piston flow, and is used to receive a signal about the liquid level and adjust the degree opening the electric control valve. 7. The exchange reaction system according to claim 1, in which the vertical reactor (2) with a fully mixed stream contains the first reactor vessel and a mixing device, comprising: a mixing rod (5) connected to the first reactor vessel, with one end extending into the interior of the first reactor vessel; a plurality of mixing blades (6) arranged symmetrically in the axial direction or radially on the mixing rod (5); preferably, the mixing device containing a set of groups of mixing blades is parallel to the direction of extension of the mixing rod (5), each of the groups of mixing blades contains a set of mixing blades (6) located on the same horizontal plane, and, more preferably , the number of groups of mixing blades is from 2 to 5, and, more preferably, the various mixing blades (6) in two adjacent groups of mixing blades alternate. 8. The exchange reaction system according to claim 7, in which the vertical reactor (2) with a completely mixed stream further comprises an internal set of spiral heating pipes (3), the internal set of spiral heating pipes (3) located inside the first reactor vessel and surrounds the device for mixing; and preferably, the internal set of spiral heating pipes (3) contains several groups of internal spiral heating pipes arranged in concentric circles, each of the internal spiral heating pipes being axially and spirally along the vertical reactor (2) with a completely mixed flow. 9. The exchange reaction system according to claim 1, in which the vertical reactor (7) with a piston flow includes a second reactor vessel and an assembled film supply unit located inside the second reactor vessel, this assembled film supply unit containing several layers of the block (12) film feeds arranged in parallel layers; preferably, the film supply unit assembly contains 4 to 40 layers of a film supply unit (12). 10. The exchange reaction system according to claim 9, in which the film supply unit comprises: porous cover (8); the bypass tray (9), which is located downstream of the porous lid (8), and in the bypass tray (9) there is a bypass hole; preferably, the porous cover (8) has a structure with the center raised up, the overflow tray overflow hole (9) is located in the center of the bypass tray (9), and even more preferably, the porous cover (8) is a conical plate in the form of an umbrella. 11. A modified polyester production system comprising an esterification system, a preliminary polycondensation system and a final polycondensation system, the modified polyester production system further comprising an in-line modifier addition system located between the esterification system and the preliminary polycondensation system in accordance with the flow rate of the material and the exchange reaction system according to any of paragraphs. from 1 to 10. 12. The modified polyester production system according to claim 11, wherein the in-line modifier adding system comprises an in-line injection device of the modifying superconcentrate and / or an in-line injection device of the modifier solution; and preferably the modulating superconcentrate inline injection device comprises a modifying superconcentrate drying system, a screw extruder and a metering pump for melt the modifying superconcentrate, which are connected in series; and The modifier solution in-line injection device comprises a reservoir for preparing a modifier solution, a reservoir for supplying a modifier solution, a dosing pump of a modifier solution and an injector of a modifier solution, which are connected in series. 13. The modified polyester production system according to claim 12, wherein the modified polyester production system further comprises a dynamic mixer located between the in-line modifier adding system and the exchange reaction system; preferably, the dynamic mixer is a 1-5 stage high shear dynamic mixer. 14. The modified polyester production system according to claim 12, wherein the modified polyester production system further comprises an oligomeric heat exchanger and a device for dispensing oligomers that are arranged in a material flow sequence between the esterification system and an in-line addition system, preferably, the oligomer delivery dispensing dispensing device comprises an oligomer pump and an oligomeric flowmeter located downstream of the oligomeric pump. 15. A method of manufacturing a modified polyester, in which the method includes the following steps: accordingly, the preparation of the suspension and modifier; and adding a suspension to the modified polyester production system according to any one of claims. 11-14 and adding a modifier to the in-line system for adding a modified polyester production system according to any one of paragraphs. 11-14 for the purpose of producing modified polyester. 16. The production method according to p. 15, in which during the production of the modifier receive a modifier having a dynamic viscosity of from 0.05 Pa · s to 1000 Pa · s. 17. The production method according to p. 16, in which: when the modified polyester production system comprises an oligomeric heat exchanger, the oligomeric heat exchanger adjusts the oligomer temperature to 180 ° C to 300 ° C; and when the modified polyester production system comprises a dynamic mixer, the dynamic mixer has a rotation speed of 50 rpm to 5000 rpm. 18. The production method according to claim 17, in which the exchange reaction system has a reaction temperature of from 180 to 300 ° C and a reaction time of from 10 minutes to 180 minutes. 19. The production method according to claim 18, in which the molten prepolymer obtained from the preliminary polycondensation system, has a characteristic viscosity in the stream from 0.10 to 0.50 dl / g; and preferably, the final polymer melt obtained from the final polycondensation system has an inherent flow viscosity of 0.50 dl / g to 1.50 dl / g. 20. Modified polyester fiber, in which the modified polyester fiber is made from a modified polyester fiber produced by the modified polyester production system according to any one of claims. 11-14. 21. The modified polyester fiber according to claim 20, wherein the modified polyester fiber has a specific tensile load of 2.5 CN / dtex to 6.0 CN / dtex, a tensile elongation of 20% to 50%, and dye uniformity of 4 to 5 class.

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