CN104258795A - Exchange reaction system, modified polyester production system containing exchange reaction system as well as modified polyester production method - Google Patents

Abstract

The invention discloses an exchange reaction system, a modified polyester production system comprising the exchange reaction system and a modified polyester production method. The exchange reaction system includes: a vertical fully mixed flow reactor and a vertical plug flow reactor, the vertical fully mixed flow reactor includes a first material inlet and a first material outlet arranged thereon; a vertical plug flow reactor Including the second material inlet and the second material outlet arranged on it; wherein, the vertical fully mixed flow reactor is arranged on the top wall of the vertical plug flow reactor, and the first material outlet communicates with the second material inlet . The exchange reaction system of the direct connection structure of the present invention can make the materials quickly and conveniently enter the vertical plug-flow reaction kettle under the action of gravity, so that the conditions of the exchange reaction are close to homogeneous, thereby improving the performance of the modifier in the polymerization process. The distribution uniformity in the main chain of the ester molecule makes the structure of the obtained modified polyester highly uniform, which is suitable for the production of high-quality fiber and film products.

Description

Exchange reaction system, modified polyester production system including same, and modified polyester production method

technical field

The invention relates to the technical field of polymer material synthesis, in particular to an exchange reaction system, a modified polyester production system comprising the exchange reaction system and a modified polyester production method.

Background technique

As one of the most important chemical synthetic materials, polyester has been widely used in the fields of fiber, packaging, engineering plastics, and medical materials. Driven by technological progress and market demand, the global polyester industry has developed rapidly in recent years, and the competition for product homogeneity has become increasingly fierce. In the face of the new competitive situation and severe environment at home and abroad, and the serious overcapacity of conventional varieties, it is the key to actively explore the road of sustainable development of the industry and accelerate the transformation and upgrading of polyester products and technologies; develop the production of differentiated polyester products Technology and equipment are the main ways to realize transformation and upgrading.

The technical approaches to develop differentiated polyester varieties mainly include chemical modification and physical modification. Chemical modification is to form a copolymer by introducing a functional modifier into the main chain of the polyester molecule, while physical modification is to uniformly mix the functional modifier with the polyester matrix to form a blend, thereby endowing the polyester with moisture absorption, resistance Combustible, antibacterial, conductive or cationic dyes can be dyed and other physical properties. The efficient dispersion of modifiers and the precise control of the addition ratio are the keys to ensure the stability of differentiated polyester production and the uniformity of product structure.

At present, before the polycondensation process, the mixing and dispersing of the modifier in the main material mainly uses the agitator of the esterification tank and the static mixer of the oligomer pipeline. The uniform mixing between the main material and the incompatible modifier will eventually lead to poor uniformity of the modified polyester structure, and the spun fibers are prone to color difference when dyed. Therefore, how to improve the uniformity of the modified polyester structure has become an urgent problem to be solved.

Contents of the invention

The invention aims to provide an exchange reaction system, a modified polyester production system comprising the same and a modified polyester production method, so as to improve the uniformity of the modified polyester structure.

In order to achieve the above object, according to one aspect of the present invention, a kind of exchange reaction system is provided, the exchange reaction system includes: vertical full mixed flow reactor and vertical plug flow reactor, vertical full mixed flow reactor, including setting The first material inlet and the first material outlet on it; the vertical plug flow reactor, including the second material inlet and the second material outlet arranged on it; wherein, the vertical full mixed flow reactor is arranged on a vertical On the top wall of the plug-flow reactor, and the first material outlet communicates with the second material inlet.

Further, the bottom wall of the vertical fully mixed flow reactor is at least partly shared with the top wall of the vertical plug flow reactor to form a shared tank wall, and the first material outlet and the second material inlet overlap and are arranged on the shared tank wall .

Further, the common kettle wall has a structure in which the middle part is sunken downward relative to the vertical fully mixed flow reactor.

Further, the vertical fully mixed flow reactor and the vertical plug flow reactor are coaxially arranged, preferably the first material outlet and the second material inlet overlap and are located on the axis of the vertical fully mixed flow reactor and the vertical plug flow reactor superior.

Further, the aspect ratio of the vertical fully mixed flow reactor is 0.5 to 3, the aspect ratio of the vertical plug flow reactor is 2 to 20, and the diameter of the vertical fully mixed flow reactor is larger than that of the vertical plug flow reactor diameter; more preferably the diameter of the vertical full mixed flow reactor is 1.05 to 5 times the diameter of the vertical plug flow reactor.

Further, the exchange reaction system further includes a liquid level cascade control system, and the liquid level cascade control system includes: a liquid level transmitter, which is used to sense the liquid level inside the vertical fully mixed flow reactor, and according to the liquid level The information sends the liquid level height signal; the electric control valve is set on the communication pipeline between the first material outlet of the vertical fully mixed flow reactor and the first material inlet of the vertical plug flow reactor, and is used to receive the liquid level height signal, And adjust the opening of the electric control valve according to the liquid level signal.

Further, the vertical fully mixed flow reaction kettle includes a first tank body and a stirrer, and the stirrer includes: a stirring rod, connected to the first tank body, and one end extends to the inside of the first tank body; a plurality of stirring paddles, axisymmetric Or radially symmetrically arranged on the stirring rod; preferably the stirrer includes multiple groups of stirring paddles arranged in parallel along the extending direction of the stirring rod, and each stirring paddle group includes a plurality of stirring paddles arranged on the same horizontal plane, more preferably the stirring paddle group The number of groups is 2 to 5 groups, more preferably the stirring blades in two adjacent groups of stirring paddles are arranged in a staggered manner.

Further, the vertical fully mixed flow reaction kettle also includes a heating inner coil assembly, which is arranged in the first kettle body and surrounds the agitator; preferably, the heating inner coil assembly includes multiple sets of concentric circles The heating inner coils are arranged spirally along the axial direction of the vertical fully mixed flow reactor.

Further, the vertical plug-flow reactor includes a second still body and a falling film assembly arranged in the second still body, the falling film assembly includes multiple falling film units arranged in parallel; preferably the falling film assembly includes 4 to 40 layers Falling film unit.

Further, the falling film unit includes: a porous cover plate; an overflow tray, which is arranged downstream of the porous cover plate along the material flow direction, and the overflow tray is provided with an overflow port; preferably, the porous cover plate has a center facing upward The structure is raised, and the overflow port of the overflow tray is located at the center of the overflow tray, more preferably the porous cover plate is a conical umbrella plate.

According to another aspect of the present invention, a modified polyester production system is also provided, including an esterification system, a precondensation system, and a final polycondensation system. The online addition system of the modifier between the precondensation system and any of the above-mentioned exchange reaction systems.

Further, the modifier online addition system includes modifier master batch online injection device and/or modifier solution online injection device; preferably modifier master batch online injection device includes modifier master batch drying system connected in sequence, Screw extruder, modifier masterbatch melt metering pump; modifier solution online injection device includes modifier solution preparation tank, modifier solution supply tank, modifier solution metering pump and modifier solution Solution syringe.

Further, the modified polyester production system also includes a dynamic mixer arranged between the modifier online addition system and the exchange reaction system; preferably, the dynamic mixer is a 1-5 stage high-shear dynamic mixer.

Further, the modified polyester production system also includes an oligomer heat exchanger and an oligomer metering device arranged between the esterification system and the online addition system according to the flow sequence of the stream, preferably the oligomer delivery metering device includes an oligomer The polymer pump and the oligomer flow meter arranged after the oligomer pump.

According to still another aspect of the present invention, a kind of preparation method of modified polyester is provided, and this preparation method comprises the following steps: preparing slurry and modifying agent respectively; Adding slurry to any one of above-mentioned modified polyester production systems , adding the modifier to the online addition system of any of the above-mentioned modified polyester production systems to obtain the modified polyester.

Further, during the process of preparing the modifying agent, a modifying agent with a dynamic viscosity of 0.05 Pa.s to 1000 Pa.s is prepared.

Further, when the modified polyester production system includes an oligomer heat exchanger, the oligomer heat exchanger adjusts the oligomer temperature to 180-300°C; when the modified polyester production system includes a dynamic mixer, The rotational speed of the dynamic mixer is 50-5000r/min.

Further, the reaction temperature of the exchange reaction system is 180-300° C., and the reaction time is 10-180 minutes.

Further, the online detection viscosity of the prepolymer melt obtained after passing through the precondensation system is 0.10-0.50 dL/g, preferably the online detection viscosity of the final polymer melt obtained after passing through the final polycondensation system is 0.50-1.50 dL/g .

According to yet another aspect of the present invention, a modified polyester fiber product is provided, which is prepared from the modified polyester fiber produced by any of the above-mentioned modified polyester fiber production systems.

Further, the breaking strength of the modified polyester fiber product is 2.5-6.0 cN/dtex, the breaking elongation is 20-50%, and the dyeing uniformity is 4-5 grades.

Applying the technical scheme of the present invention, by setting the vertical full mixed flow reactor on the top wall of the vertical plug flow reactor, the exchange reaction system of this directly connected structure enables the materials to achieve high efficiency in the vertical full mixed flow reactor. After the mixed state, it can quickly and conveniently enter the vertical plug-flow reactor under the action of gravity, which greatly shortens the time for the material to go from the vertical full-mixed-flow reactor to the vertical plug-flow reactor, and makes the material in the vertical plug-flow reactor in the early stage The nearly homogeneous exchange reaction state in the fully mixed flow reactor can be transferred to the vertical plug flow reactor in a relatively short period of time for the subsequent near homogeneous exchange reaction, which makes the conditions of the exchange reaction easy to control and can Improve the uniformity of the distribution of modifiers in the main chain of polyester molecules, so that the obtained modified polyester structure is highly uniform, suitable for the production of high-quality fiber and film products.

Description of drawings

The accompanying drawings constituting a part of the present application are used to provide a further understanding of the present invention, and the schematic embodiments and descriptions of the present invention are used to explain the present invention, and do not constitute an improper limitation of the present invention. In the attached picture:

Fig. 1 shows the exchange reaction system provided according to a typical embodiment of the present invention;

Fig. 2 shows the technological process of the modified polyester production system provided according to a typical embodiment of the present invention;

Fig. 3 shows the modified polyester production system provided according to a typical embodiment of the present invention;

FIG. 4 shows the DSC scanning curves of the modified polyester prepared according to Example 1 and Comparative Example 1 of the present invention.

Detailed ways

It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and examples.

As mentioned in the background art, in the prior art, there is a technical problem that incompatible modifiers are difficult to mix uniformly with the main materials, resulting in poor uniformity of the modified polyester structure. In order to improve the above-mentioned defects of the prior art, the present invention provides a kind of exchange reaction system, as shown in Figure 1, this exchange reaction system comprises: vertical fully mixed flow reactor 2 and vertical plug flow reactor 7, vertical The full mixed flow reactor 2 includes the first material inlet and the first material outlet arranged thereon; the vertical plug flow reactor 7 includes the second material inlet and the second material outlet arranged thereon; wherein, the vertical full The mixed-flow reactor is arranged on the top wall of the vertical plug-flow reactor, and the first material outlet communicates with the second material inlet.

The above-mentioned exchange reaction system of the present invention, through the exchange reaction system of this directly connected structure that the vertical fully mixed flow reactor is arranged on the top wall of the vertical plug flow reactor, the material reaches the maximum level in the vertical full mixed flow reactor. After the high-efficiency mixing state, it can quickly and conveniently enter the vertical plug-flow reactor under the action of gravity, which greatly shortens the time for the material to go from the vertical full-mixed-flow reactor to the vertical plug-flow reactor, and makes the material in the early stage. The nearly homogeneous exchange reaction state in the vertical fully mixed flow reactor can be transferred to the vertical plug flow reactor for subsequent near homogeneous exchange reaction in a relatively short period of time, making the conditions of the exchange reaction easy to control, and It can improve the distribution uniformity of the modifier in the main chain of the polyester molecule, so that the structure of the obtained modified polyester is highly uniform, and is suitable for the production of high-quality fiber and film products.

The above-mentioned exchange reaction system of the present invention realizes the direct connection of the two kinds of reactors by arranging the vertical fully mixed-flow reactor 2 on the top wall of the plug-flow reactor. Compared with two kinds of reactors connected by pipes, the reaction conditions of this directly connected exchange reaction system are easy to control. In order to further optimize the above-mentioned structure, the top wall part of the vertical fully mixed flow reactor and the vertical plug flow reactor can be shared to form a common wall, while the first material outlet and the second material inlet overlap each other, and are arranged on the common wall. on the wall. This one-piece exchange reaction system not only reduces the production cost, but also shortens the flow cycle of materials between the vertical fully mixed flow reactor and the vertical plug flow reactor, so that the materials can quickly enter the vertical flat flow reactor after being mixed evenly. In the plug-flow reactor, the uniform distribution of the modifier in the main chain of the polyester molecule can be realized.

In the above-mentioned exchange reaction system of the present invention, the shared wall of the vertical full-mixed flow reactor and the vertical plug-flow reactor has a structure in which the middle part is sunken downward relative to the vertical full-mixed-flow reactor. This downwardly sunken structure is convenient The materials in each place flow into the plug-flow reactor from the first material outlet relatively smoothly, so as to maintain the relative uniformity of the materials in each place.

In a preferred embodiment of the present invention, the above-mentioned exchange reaction system adopts a vertical fully mixed-flow reactor and a plug-flow reactor coaxially arranged. This coaxial arrangement can make the structure of the exchange reaction system more stable, and relatively Save floor space.

Comprehensively considering the mixing degree of materials and the optimization effect of the residence time on the exchange reaction, in the above-mentioned exchange reaction system of the present invention, the length-to-diameter ratio of the vertical fully mixed flow reactor 2 is preferably 0.5 to 3, and the vertical plug flow reactor vertical The length-to-diameter ratio of the vertical plug-flow reactor 7 is 2 to 20, and the diameter of the vertical full-mixed-flow reactor 2 is greater than the diameter of the vertical plug-flow reactor 7; the diameter of the vertical full-mixed-flow reactor 2 is more preferred It is 1.05 to 5 times the diameter of the vertical plug flow reactor 7. When the length-to-diameter ratio of the vertical fully mixed-flow reactor is within the above range, it is beneficial to mix the materials everywhere without dead ends; the vertical plug-flow reactor with the length-to-diameter ratio within the above-mentioned range has a small diameter and a high The tower structure with aspect ratio can increase the potential difference, which is convenient for materials to flow from top to bottom in the reactor by using their own gravity.

On the basis of the above, the diameter of the vertical fully mixed flow reactor 2 is greater than the diameter of the vertical plug flow reactor 7; more preferably, when the diameter of the vertical fully mixed flow reactor 2 is the diameter of the vertical plug flow reactor When it is 1.05 to 5 times that of the vertical fully mixed flow reactor, it can not only take advantage of the large diameter and low aspect ratio of the vertical fully mixed flow reactor, which is conducive to more uniform mixing of materials everywhere, without the advantage of dead ends; The tower structure with aspect ratio can increase the potential difference, realize the beneficial effect of facilitating the flow of materials from top to bottom in the reactor by using their own gravity, and save the floor space of the reaction system.

In order to make the materials mix more fully in the vertical fully mixed flow reactor, in a preferred embodiment of the present invention, the above-mentioned exchange reaction system also includes a liquid level cascade control system, and the liquid level cascade control system includes a liquid level cascade control system Level transmitter and electric control valve, liquid level transmitter, used to sense the liquid level inside the vertical fully mixed flow reactor, and send the liquid level signal according to the liquid level information; the electric control valve, set in the vertical The connecting pipeline between the first material outlet of the fully mixed flow reactor and the first material inlet of the plug flow reactor is used to receive the liquid level signal and adjust the opening of the electric control valve according to the liquid level signal. By using the above-mentioned liquid level transmitter to sense the liquid level height of the material in the vertical fully mixed flow reactor in real time, when the liquid level changes, the opening of the electric regulating valve is controlled by an electric signal to realize the vertical full mixed flow reactor. Efficient operation and efficient and uniform mixing of materials.

In the above-mentioned exchange reaction system of the present invention, the height of the liquid level in the vertical full-mixed flow reactor, i.e. the liquid level, is required according to the blend of modifying agent and polyester oligomer to form a homogeneous fluid by exchange reaction determined by the dwell time. In actual production, the liquid level in the vertical fully mixed flow reactor can be adjusted reasonably according to the required residence time.

In the above-mentioned exchange reaction system of the present invention, the vertical fully mixed flow reactor mainly realizes the fully mixed flow mixing of materials, therefore, all vertical fully mixed flow reactors that can realize the above functions are suitable for the present invention. In the present invention, the above-mentioned vertical fully mixed flow reaction kettle includes a first kettle body and a stirrer, and the stirrer stirs the materials so that the materials can be mixed efficiently and uniformly. In the present invention, the agitator used comprises a stirring rod 5 and a plurality of stirring rods 6, the stirring rod 5 is connected to the first kettle body, and one end extends to the inside of the first kettle body; the plurality of stirring rods 6 are axisymmetric or Radially symmetrically arranged on the stirring rod 5 . The stirring rod 5 is connected to the first kettle body and driven by a motor arranged outside the first kettle body.

According to the strength of the required stirring, preferably a plurality of stirring rods 6 are axisymmetrically or radially symmetrically arranged on the stirring rod 5, so as to achieve uniform stirring and efficient uniform mixing of the materials in the first kettle body. The stirring rod 6 provided in the above-mentioned manner of the present invention has a strong stirring effect, and can make the modifying agent in the material evenly disperse in the polyester oligomer in the form of a microscale, thereby making the polyester oligomer and the modifying agent The exchange reaction between them is close to a homogeneous reaction, which improves the exchange reaction speed, shortens the reaction time, and effectively restricts the occurrence of side reactions such as thermal degradation of the modifier.

In the above-mentioned preferred embodiment, it is further preferred that the agitator includes multiple groups of agitating paddles arranged in parallel along the extension direction of the stirring rods 5, and each agitating paddle group includes a plurality of agitating rods 6 arranged on the same horizontal plane, so as to achieve different The material at the liquid level and the material at the same liquid level are fully mixed and evenly mixed. In actual production, the number of the above-mentioned stirring paddle groups can be adjusted appropriately according to the amount of materials usually processed. In the present invention, the number of stirring blade groups is preferably 2 to 5. More preferably, the stirring rods 6 in two adjacent sets of stirring paddles are arranged in a staggered manner, so that the flow process of materials passing through different adjacent two sets of stirring paddles is relatively lengthened, so that the stirring and mixing effect is better and the side reactions are less.

In the above-mentioned exchange reaction system of the present invention, there is no special requirement for the heating equipment inside the vertical fully mixed flow reactor, as long as the reaction temperature required by the materials can be met. In a preferred embodiment of the present invention, the above-mentioned vertical fully mixed flow reaction kettle further includes a heating inner coil assembly, and the heating inner coil assembly is arranged in the first kettle body and is arranged around the agitator. The heating inner plate assembly is arranged around the agitator, which can keep the material at a relatively uniform temperature while stirring and mixing, so as to achieve uniformity of mixing, and then make the early exchange reaction close to a homogeneous reaction state.

In the above embodiment, it is further preferred that the heating inner coil assembly includes multiple sets of heating inner coils arranged concentrically, and each heating inner coil is arranged spirally along the axial direction of the vertical fully mixed flow reactor. This arrangement enables the material to be heated more evenly in radial and axial directions. The above-mentioned heating inner coil of the present invention adopts an independent secondary heat medium system. By adjusting the temperature and flow rate of the heat medium in the heating coil, the temperature of the reaction material in the reaction system can be quickly adjusted, and the occurrence of thermal degradation side reactions of the modifier can be effectively controlled. .

In the above-mentioned exchange reaction system of the present invention, the plug-flow reactor can adopt the plug-flow reactor commonly used in the field, as long as the plug-flow mixing effect can be realized for the materials. In a preferred embodiment of the present invention, the above-mentioned plug-flow reactor includes a second tank body and a falling film module arranged in the second tank body, and the falling film module includes multiple layers of falling film units 12 arranged in parallel.

By arranging the multi-layer falling film unit 12 in the second tank body, the homogeneous fluid formed by the previous exchange reaction can enter the lower layer of the plug-flow reactor under the action of the pressure difference, and then use its own gravity to pass through the multi-layered reactor. The falling film module composed of layered falling film units 12 flows downward in the way of plug flow, and this flow mode can realize the first-in-first-out of the reaction materials. Therefore, the extent of the exchange reaction can be effectively controlled by adjusting the reaction temperature and residence time of the materials in the plug flow reactor, and a modified polyester oligomer with uniform structure can be obtained.

In the above embodiments of the present invention, the residence time of the reactant flow material is adjusted by adjusting the number of layers of the falling film unit 12 arranged in the plug flow reactor. The more layers of the falling film unit 12, the smaller the difference in the residence time between the materials, and the better the uniformity of the exchange reaction. In the present invention, preferably the falling film module comprises 5-60 layers of falling film units 12, more preferably 10-30 layers.

In a preferred embodiment of the present invention, the falling film unit 12 of the above-mentioned plug flow reactor includes a porous cover plate 8 and an overflow tray 9, wherein the overflow tray 9 is arranged on the porous cover plate along the material flow direction 8, and an overflow port is provided on the overflow tray 9. The porous cover plate 8 can divide the material fluid and play the role of static mixing. In a more preferred embodiment of the present invention, the above-mentioned perforated cover plate 8 has a structure with the center facing upward, which is more convenient for the material fluid to disperse and flow around quickly. The overflow port of the overflow tray 9 is located at the center of the overflow tray 9. This arrangement is more convenient for the material to flow to the porous cover plate 8 of the next falling film unit 12 under the action of its own gravity, and then disperse quickly. to the perimeter of the reamer.

In the above-mentioned preferred embodiment, the porous cover plate 8 is further preferably a conical umbrella plate, which has a certain taper, which is more convenient for the overflow of the material fluid from the overflow tray 9 of the falling film unit 12 on the upper floor. The outlet overflows to the center of the conical umbrella plate of the falling film unit 12 of the next layer, and then flows rapidly around the cover plate under the action of gravity. That is, the overflow port of the overflow tray 9 is facing the conical top of the conical umbrella plate, so that the material overflowing from the overflow tray 9 to the conical top of the conical umbrella plate will flow along a certain tapered path under the action of gravity. Umbrella panels flow around more quickly.

In another typical implementation of the present invention, a kind of modified polyester production system is also provided, as can be seen from the flowchart of producing modified polyester shown in Figure 2, this modified polyester production In addition to the commonly used esterification system, precondensation system and final polycondensation system in the polyester production process, the system also includes an online modifier addition system and the above-mentioned any An exchange reaction system.

The above-mentioned modified polyester production system provided by the present invention can not only realize the modification of the modifier in polyester oligomerization by adding the modifier online addition system and any of the above-mentioned exchange reaction systems in the commonly used polyester production system. In addition, the modifier and the polyester oligomer can be exchanged to realize the uniform distribution of the modifier in the main chain of the polyester oligomer, so that the obtained modified polyester fiber structure is highly uniform , can be used to produce high-quality fiber and film products.

In the above-mentioned modified polyester production system of the present invention, the modifying agent online addition system is a device for adding the required modifying agent in real time to the polyester oligomers that are sent out from the esterification system through the esterification reaction. . In actual production, according to the different modifiers to be added, the modifier online adding device commonly used in this field can be properly adjusted and then applied to the present invention. In a preferred embodiment of the present invention, as shown in FIG. 3 , the modifier online addition system includes an online modifier masterbatch injection device and/or a modifier solution online injection device. The modifier master batch online injection device can realize the online addition of the solid particle modifier, and the modifier solution online injection device can realize the online addition of the liquid modifier solution, and set the above two modifiers online injection at the same time The device can realize simultaneous online addition of two or more liquid and solid modifiers.

In the above embodiments of the present invention, the modifier masterbatch online injection device can make reasonable adjustments to the existing solid particle modifier online addition device, as long as the required solid particle modifier can be added online . In the same way, the on-line injecting device of the modifier solution can be applied to the present invention only by making reasonable adjustments to the existing on-line adding device of the liquid modifier. In a more preferred embodiment of the present invention, the above-mentioned modifying agent master batch online injection device includes a modifier master batch drying system, a screw extruder, a modifier master batch melt metering pump connected in sequence; The agent solution online injection device comprises a modifier solution preparation tank, a modifier solution supply tank, a modifier solution metering pump and a modifier solution injector connected in sequence.

The modifier masterbatch online injection device with the above-mentioned structure in the present invention can effectively connect the production and processing process of the modifier masterbatch with the device that needs to add the modifier, and can also control the modifier that needs to be added. The amount of modifier masterbatch is measured to achieve precise addition of modifiers. Similarly, the modifier solution online injection device in the above preferred embodiments of the present invention can realize real-time modulation, supply, metering and precise addition of the required modifier solution at the same time.

Compared with the prior art, the mixing and dispersing of the modifier in the polyester oligomer is mainly realized by the agitator of the esterification system and the static mixer of the oligomer pipeline, in the above-mentioned modified polyester production system of the present invention It also includes a dynamic mixer as shown in Figure 3, which realizes the homogeneous mixing and dispersion of the modifier in the polyester oligomer by means of dynamic mixing, so as to achieve almost homogeneous physical blending. In a preferred embodiment of the present invention, the above-mentioned dynamic mixer is a 1-5 stage high-shear dynamic mixer, and the high-shear dynamic mixer has a better mixing effect on materials than ordinary dynamic mixers.

In the modified polyester production system of the present invention, the amount of polyester oligomers that can be produced can also be estimated by the amount of raw materials initially entering the esterification system, and then the amount of modifier required can be estimated. If you want to grasp the amount of polyester oligomers more accurately, so that you can more accurately measure the amount of modifying agent that needs to be added, the above-mentioned modified polyester production system of the present invention can also include setting in the esterification process according to the flow sequence of materials. Oligomer heat exchanger and oligomer metering device between the system and the in-line addition system. The oligomer heat exchanger can regulate the temperature of polyester oligomers from the esterification system to facilitate the addition and mixing of modifiers. The oligomer metering device can accurately measure the amount of polyester oligomers that need to be added with modifiers. More preferably, the oligomer delivery metering device includes an oligomer pump and an oligomer flowmeter arranged behind the oligomer pump.

In yet another typical embodiment of the present invention, a method for preparing modified polyester is also provided. The preparation method includes the following steps: preparing slurry and modifier respectively; adding the slurry to any of the above modified In the permanent polyester production system, the modifier is added to the online addition system of any modified polyester production system to obtain the modified polyester.

The preparation method of the above-mentioned modified polyester of the present invention is prepared by utilizing the above-mentioned modified polyester production system, so that the modifier is evenly distributed in the main chain of the polyester molecule, so that the prepared modified polyester has a high structure Uniform, suitable for the production of high quality fiber and film products.

In the above-mentioned preparation method of the present invention, the preparation of the slurry is carried out by using dibasic acid and dibasic alcohol as raw materials according to conventional methods in the art. Among them, the most commonly used dibasic acid is terephthalic acid, and the dibasic alcohol is selected from at least one of ethylene glycol, propylene glycol, butanediol or cyclohexanedimethanol. The preparation process of the modifier varies according to the type of the modifier. In a preferred embodiment of the present invention, during the process of preparing the modifying agent, a modifying agent with a dynamic viscosity of 0.05 Pa.s to 1000 Pa.s is prepared. Among them, the preferred dynamic viscosity of the modifier solution is 0.05-5 Pa.s, and the preferred dynamic viscosity of the modifier masterbatch melt is 5-1000 Pa.s. Modifiers within this dynamic viscosity range can be uniformly mixed with polyester oligomers through a dynamic mixer.

In the above-mentioned preparation method of the present invention, the reaction temperature of the esterification system is the temperature commonly used in the esterification reaction in the field, that is, 200-280° C., and the degree of polymerization of the polyester oligomer after the esterification reaction is 1-8. Polyester oligomers with a lower degree of polymerization are easier to achieve blending or copolymerization with modifiers.

In the above preparation method of the present invention, when the modified polyester production system includes an oligomer heat exchanger, the oligomer heat exchanger adjusts the temperature of the oligomer to 180-300°C. Adjusting the temperature of the oligomer to the above temperature range can make the temperature of the polyester oligomer close to the temperature of the modifier to be added, and reduce adverse reactions caused by temperature differences.

In the above preparation method of the present invention, when the modified polyester production system includes a dynamic mixer, the rotational speed of the dynamic mixer is 50-5000 r/min. The rotation speed within the above range can achieve efficient mixing of polyester oligomer and modifier.

In the above-mentioned preparation method of the present invention, the exchange reaction system has slight differences in reaction temperature and reaction time according to the difference of the material in which the exchange reaction actually occurs. In a preferred embodiment of the present invention, the temperature of the above-mentioned exchange reaction is 180-300° C., and the reaction time is 10-180 min. Controlling the temperature and reaction time of the exchange reaction within the above range can realize the efficient dispersion of the modifier in the polyester oligomer and the near-homogeneous reaction of the exchange reaction, so that the modifier can be dispersed in the polyester low polymer as uniformly as possible. on the main chain of the polymer. In addition, by adjusting the reaction temperature and residence time of the materials in the plug flow reactor of the exchange system, the extent of the exchange reaction can be effectively controlled to obtain a modified polyester oligomer with uniform structure.

In the above preparation method of the present invention, the reaction temperature of the precondensation reaction system is 200-300° C., which is commonly used in the field of precondensation reaction. The structurally uniform modified polyester oligomer obtained by the exchange reaction in the preparation method of the present invention has an online detection intrinsic viscosity of the prepolymer melt obtained after the precondensation reaction is 0.10～0.50dL/g, so as to meet the following The viscosity requirement of the final polycondensation is the same, in the preparation method of the present invention, the conditions of the final polycondensation reaction are also common conditions of the final polycondensation reaction in the field. In a preferred embodiment of the present invention, the reaction temperature of the final polycondensation reaction system is 200-300°C. The modified polyester oligomer with uniform structure obtained by the exchange reaction in the preparation method of the present invention, after precondensation and final polycondensation, obtains a final polymer melt with an on-line detection viscosity of 0.50～1.50dL/g, so as to satisfy Viscosity requirements for subsequent spinning.

In another typical embodiment of the present invention, a modified polyester fiber product is also provided, which is prepared from the modified polyester produced by any of the above-mentioned modified polyester production systems. The breaking strength of the modified polyester fiber product provided by the present invention is 2.5-6.0cN/dtex, the breaking elongation is 20-50%, and the dyeing uniformity is 4-5 grades. Not only the breaking strength and breaking elongation of the fiber It can meet the requirements of subsequent weaving, and has higher dyeing uniformity than modified polyester fiber products prepared in the prior art, indicating that the modified polyester fiber products provided by the present invention have higher structural uniformity.

The beneficial effects of the present invention will be further described below in conjunction with specific examples.

It should be noted that the embodiment of the present invention carries out the preparation of the modified polyester according to the process shown in Figure 2, and further performs the addition of the modifying agent and the dynamic mixing of physical blending according to the process shown in Figure 3, and enters The exchange reaction system shown in Fig. 1 performs the exchange reaction. In Fig. 1, the label 1 is the material inlet to be exchanged, 2 is the vertical fully mixed flow reactor, 3 is the heating inner coil assembly, 4 is the motor of the agitator, 5 is the stirring rod, and 6 is axisymmetrically arranged Stirring paddle, 7 is a plug-flow reaction kettle, 8 is a conical umbrella plate, 9 is an overflow tray, 10 is a material outlet after the exchange reaction, 11 is a stirrer, and 12 is a falling film unit.

Example 1

The slurry formulated with terephthalic acid and ethylene glycol is continuously and uniformly transported at a flow rate of 2964kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 4, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably flowed from Extracted from the esterification kettle.

The oligomer from the esterification reaction system is cooled to 250°C by the Sulzer type heat exchanger, and then enters the dynamic mixer together with the modifier polycaprolactam masterbatch melt from the modifier masterbatch online injection device, and the polycaprolactam The injection temperature of the masterbatch melt is 250°C, the injection flow rate is 125kg/h, and the dynamic viscosity is 180Pa.s. The process flow of polycaprolactam masterbatch injection is as follows: the polycaprolactam masterbatch is dried by the modifier masterbatch drying system, It is melted by the screw extruder, and the metering flow is controlled by the modifier masterbatch melt metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device, and then directly injected into the feed pipe of the dynamic mixer.

The oligomer and modifier polycaprolactam masterbatch melts are evenly mixed by a 5-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The length-to-diameter ratio of the vertical fully mixed-flow reactor in the reaction system is 1.5, the number of stirring paddles is 3 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 10, and the number of falling film unit layers is 20. The diameter of the mixed-flow reactor is twice that of the vertical plug-flow reactor. After the melt blend of oligomer and modifier polycaprolactam masterbatch is obtained through ester-amide exchange reaction in the exchange reaction system to obtain ethylene terephthalate/caprolactam copolymer, it is directly transported by the oligomer pump to The precondensation reaction system carries out the precondensation reaction, wherein the reaction temperature of the exchange reaction system is 260° C., and the reaction time is 90 minutes.

The precondensation reaction system consists of a vertical polycondensation tank, and the reaction temperature of the precondensation tank is 270°C. When the prepolymer intrinsic viscosity reaches 0.30dL/g, the prepolymer pump is continuously and stably extracted from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 280°C. When the intrinsic viscosity of the final polymer reaches 0.80dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a hydrophilic polyester fiber: the breaking strength is 4.1 cN/dtex, the breaking elongation is 38%, and the dyeing uniformity is grade 5. The dyeing results of the fibers show that the modifier polycaprolactam molecular segments are evenly distributed in the main chain of the polyester molecule, so that the structure of the hydrophilic polyester is uniform, and the fiber dyeing has no color difference.

Example 2

The slurry formulated with terephthalic acid and ethylene glycol is continuously and uniformly transported at a flow rate of 2964kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 261°C. The catalyst antimony acetate solution with a concentration of 3.5wt% was continuously and evenly injected into the esterification kettle at a flow rate of 41.5kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 4, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from Extracted from the esterification kettle.

The oligomer from the esterification reaction system is cooled to 230°C by a Sulzer type heat exchanger, and then mixed with the modifier diethylene glycol isophthalate-5-sodium sulfonate from the modifier solution online injection device The solutions enter the dynamic mixer together. The concentration of diethylene glycol isophthalate-5-sodium sulfonate solution is 25wt%, the injection temperature is 90°C, the injection flow rate is 186kg/h, and the dynamic viscosity is 0.1Pa.s, wherein diethylene isophthalate The technological process of injection of glycol ester-5-sodium sulfonate solution is as follows: add diethylene glycol isophthalate-5-sodium sulfonate esterification solution into the modifier solution preparation tank and prepare it with ethylene glycol The solution with a concentration of 25wt% is then transferred to the modifier solution supply tank through the potential difference, and the metering flow is controlled by the modifier solution injector through the modifier solution metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device. Inject into the dynamic mixer feed line.

Oligomer and modifying agent diethylene glycol isophthalate-5-sodium sulfonate solution enter the exchange reaction system after being uniformly mixed through a 3-stage high-shear dynamic mixer, and the temperature of the dynamic mixer is 230 ℃, rotating speed 1000r/min, the length-to-diameter ratio of the vertical full-mixed flow reactor of the exchange reaction system is 1, the number of stirring paddles is 2 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 4, and the falling film The number of unit layers is 8, and the diameter of the vertical fully mixed flow reactor is 1.2 times the diameter of the vertical plug flow reactor. The blend of oligomer and modifying agent diethylene glycol isophthalate-5-sodium sulfonate is obtained by transesterification reaction in the exchange reaction system to obtain ethylene terephthalate/diethylene terephthalate After the ethylene glycol ester-5-sulfonate sodium oligomer is directly transported by the oligomer pump to the precondensation reaction system for precondensation reaction, the reaction temperature of the exchange reaction system is 235°C and the reaction time is 40min.

The pre-condensation reaction system consists of a vertical pre-condensation tank, wherein the temperature of the reactants in the pre-condensation tank is 260°C. When the intrinsic viscosity of the prepolymer reaches 0.15dL/g, the prepolymer pump is continuously and stably withdrawn from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 275°C. When the intrinsic viscosity of the final polymer reaches 0.50dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a cationic dye-dyeable polyester fiber: the fiber breaking strength is 3.0 cN/dtex, the breaking elongation is 32%, and the dyeing uniformity is 4.5. The dyeing results of the fibers showed that the modifying agent diethylene glycol isophthalate-5-sodium sulfonate segment was evenly distributed in the main chain of the polyester molecule, so that the structure of the cationic dyeable polyester was uniform, and the fiber dyeing was free. chromatic aberration.

Example 3

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2808kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 260°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 3, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably flowed from Extracted from the esterification kettle.

The oligomer from the esterification reaction system is cooled to 240°C by a multi-tubular heat exchanger and enters together with the modifier polybutylene terephthalate masterbatch melt from the modifier masterbatch online injection device Dynamic mixer, the injection temperature of polybutylene terephthalate masterbatch melt is 240°C, the injection flow rate is 250kg/h, and the dynamic viscosity is 450Pa.s, of which polybutylene terephthalate masterbatch The injection process is as follows: the polybutylene terephthalate masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and delivered and measured by the modifier masterbatch melt metering pump according to the oligomer The flow ratio of the output oligomer of the device is directly injected into the feed pipeline of the dynamic mixer after controlling the metered flow.

The oligomer and modifier polybutylene terephthalate masterbatch melt are uniformly mixed by a 5-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 240 ° C, The rotation speed is 1500r/min, the length-to-diameter ratio of the vertical fully mixed-flow reactor of the exchange reaction system is 2, the number of stirring paddles is 4 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 15, and the number of falling film unit layers It is 30 layers, and the diameter of the vertical fully mixed flow reactor is 1.5 times the diameter of the vertical plug flow reactor. The melt blend of oligomer and modifier polybutylene terephthalate masterbatch is obtained through transesterification reaction in the exchange reaction system to obtain ethylene terephthalate/butylene terephthalate After the copolymerization, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the reaction temperature of the exchange reaction system is 250°C, and the reaction time is 150min.

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank, wherein the temperature of the reactants in the first pre-condensation tank is 260°C, and the temperature of the reactants in the second pre-condensation tank is 265°C. When the intrinsic viscosity of the prepolymer reaches 0.40dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 270°C. When the intrinsic viscosity of the final polymer reaches 0.90dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a disperse dye normal-pressure dyeable polyester fiber: the breaking strength is 4.2cN/dtex, the breaking elongation is 45%, and the dyeing uniformity is 4.5 grades. The dyeing results of the fiber show that the polybutylene terephthalate molecular segment of the modifying agent is evenly distributed in the main chain of the polyester molecule, so that the structure of the disperse dyeable polyester under normal pressure is uniform, and the fiber dyeing has no color difference.

Example 4

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2496kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank for esterification For the reaction, the reaction temperature of the first esterification tank is 265°C, and the reaction temperature of the second esterification tank is 268°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 8, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from The second esterification tank is taken out.

The oligomer from the esterification reaction system is heated to 300°C through a multi-tubular heat exchanger and then together with the modifier polycyclohexanedimethanol terephthalate masterbatch melt from the modifier masterbatch online injection device Entering the dynamic mixer, the injection temperature of the polycyclohexanedimethanol terephthalate masterbatch melt is 300°C, the injection flow rate is 500kg/h, and the dynamic viscosity is 300Pa.s, of which polycyclohexanedimethanol terephthalate The process flow of ester masterbatch injection is as follows: the masterbatch of polycyclohexanedimethanol terephthalate is dried by the modifier masterbatch drying system, melted by the screw extruder, and passed through the modifier masterbatch melt metering pump according to the low The flow ratio of the output oligomer of the polymer delivery metering device is directly injected into the feed pipe of the dynamic mixer after controlling the metering flow rate.

The oligomer and modifier polycyclohexanedimethanol terephthalate masterbatch melt is uniformly mixed by a 3-stage high-shear dynamic mixer and then enters the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 300°C , The rotating speed is 2000r/min, the aspect ratio of the vertical fully mixed flow reactor of the exchange reaction system is 3, the number of stirring paddle groups is 5 groups, the aspect ratio of the vertical plug flow reactor is 12, and the falling film unit layer The number is 24 layers, and the diameter of the vertical fully mixed flow reactor is 1.8 times the diameter of the vertical plug flow reactor. The melt blend of oligomer and modifier polycyclohexanedimethanol terephthalate masterbatch is obtained through transesterification reaction in the exchange reaction system to obtain ethylene terephthalate/cyclohexanedimethanol terephthalate After the methanol ester copolymer is directly transported by the oligomer pump to the precondensation reaction system for precondensation reaction, the reaction temperature of the exchange reaction system is 300°C and the reaction time is 100min.

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank, wherein the temperature of the reactants in the first pre-condensation tank is 295°C, and the temperature of the reactants in the second pre-condensation tank is 290°C. When the intrinsic viscosity of the prepolymer reaches 0.20dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 290°C. When the intrinsic viscosity of the final polymer reaches 0.70dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a disperse dye normal-pressure dyeable polyester fiber: the breaking strength is 4.8cN/dtex, the breaking elongation is 25%, and the dyeing uniformity is grade 4. The dyeing results of the fibers show that the molecular segments of the modifier polycyclohexanedimethanol terephthalate are evenly distributed in the main chain of the polyester molecule, so that the polyester structure can be dyed uniformly by disperse dyes under normal pressure, and the fiber dyeing has no color difference.

Example 5

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2784kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank for esterification For the reaction, the reaction temperature of the first esterification tank is 265°C, and the reaction temperature of the second esterification tank is 268°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 6, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably flowed from The second esterification tank is taken out.

The oligomer from the esterification reaction system is heated up to 290°C by a Sulzer type heat exchanger, and then enters together with the modifier polyethylene naphthalate masterbatch melt from the modifier masterbatch online injection device Dynamic mixer, the injection temperature of polyethylene naphthalate masterbatch melt is 290°C, the injection flow rate is 750kg/h, and the dynamic viscosity is 600Pa.s, of which polyethylene naphthalate masterbatch is injected The technological process is as follows: the polyethylene naphthalate masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and output by the modifier masterbatch melt metering pump according to the oligomer delivery metering device. The flow ratio of the polymer is directly injected into the feed pipe of the dynamic mixer after controlling the metering flow.

The oligomer and modifier polyethylene naphthalate masterbatch melts are uniformly mixed by a 3-stage high-shear dynamic mixer, and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 290 ° C, the speed 5000r/min, the length-to-diameter ratio of the vertical fully mixed-flow reactor of the exchange reaction system is 2, the number of stirring paddles is 4 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 20, and the number of falling film unit layers is 40 layers, the diameter of the vertical fully mixed flow reactor is three times the diameter of the vertical plug flow reactor. The melt blend of the oligomer and the modifier polyethylene naphthalate masterbatch undergoes transesterification reaction in the exchange reaction system to obtain ethylene terephthalate/ethylene naphthalate copolymer Finally, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the reaction temperature of the exchange reaction system is 290°C, and the reaction time is 180min. .

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank. The temperature of the reactants in the first pre-condensation tank is 280°C, and the temperature of the reactants in the second pre-condensation tank is 285°C. When the intrinsic viscosity of the prepolymer reaches 0.20dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 290°C. When the intrinsic viscosity of the final polymer reaches 0.65dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a high-modulus polyester fiber: the breaking strength is 6.0 cN/dtex, the breaking elongation is 24%, and the dyeing uniformity is grade 4. The dyeing results of the fibers show that the polyethylene naphthalate molecular segment of the modifier is evenly distributed in the main chain of the polyester molecule, so that the structure of the high modulus polyester is uniform, and the fiber dyeing has no color difference.

Example 6

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2784kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank for esterification For the reaction, the reaction temperature of the first esterification tank is 260°C, and the reaction temperature of the second esterification tank is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 5, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably flowed from The second esterification tank is taken out.

The oligomer from the esterification reaction system is cooled to 230°C by a Sulzer heat exchanger, and then enters the dynamic Mixer, the injection temperature of the polytrimethylene terephthalate masterbatch melt is 230°C, the injection flow rate is 750kg/h, and the dynamic viscosity is 150Pa.s. The process flow of the polytrimethylene terephthalate masterbatch injection is as follows : Polytrimethylene terephthalate masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and the flow rate of the oligomer is output by the modifier masterbatch melt metering pump according to the oligomer delivery metering device The proportional control metering flow is directly injected into the feed pipe of the dynamic mixer.

The oligomer and modifier poly(trimethylene terephthalate) masterbatch melt is uniformly mixed by a 4-stage high-shear dynamic mixer and then enters the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 230°C and the speed is 4000r/min, the length-to-diameter ratio of the vertical fully mixed flow reactor of the exchange reaction system is 3, the number of stirring paddles is 5 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 18, and the number of falling film unit layers is 36 The diameter of the vertical fully mixed flow reactor is 4 times that of the vertical plug flow reactor. After the melt blend of the oligomer and the modifier polytrimethylene terephthalate masterbatch is obtained through the transesterification reaction in the exchange reaction system to obtain the ethylene terephthalate/trimethylene terephthalate copolymer, The oligomer pump is directly transported to the precondensation reaction system for precondensation reaction, wherein the reaction temperature of the exchange reaction system is 230°C, and the reaction time is 160min.

The precondensation reaction system consists of a vertical precondensation reactor, and the reaction temperature of the precondensation reactor is 245°C. When the intrinsic viscosity of the prepolymer reaches 0.40dL/g, the prepolymer pump is continuously and stably withdrawn from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 255°C. When the intrinsic viscosity of the final polymer reaches 0.95dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a disperse dye normal pressure dyeable polyester fiber: the breaking strength is 3.2cN/dtex, the elongation at break is 50%, the disperse dye normal pressure dyeing rate is 95%, and the dyeing uniformity is 4.5 grades. The dyeing results of the fiber show that the polytrimethylene terephthalate molecular segment of the modifying agent is evenly distributed in the main chain of the polyester molecule, so that the structure of the polyester dyeable under normal pressure by the disperse dye is uniform, and the fiber dyeing has no color difference.

Example 7

The slurry formulated with terephthalic acid and ethylene glycol is continuously and uniformly transported at a flow rate of 2964kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 7, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from Extracted from the esterification kettle.

The oligomer from the esterification reaction system is heated to 270°C through a single-tube heat exchanger, and then enters dynamic mixing with the modifier polyhexamethylene adipamide masterbatch melt from the modifier masterbatch online injection device The injection temperature of polyhexamethylene adipamide masterbatch melt is 270°C, the injection flow rate is 125kg/h, and the dynamic viscosity is 250Pa.s. The process flow of polyhexamethylene adipamide masterbatch injection is as follows: The polyhexamethylene adipamide masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and the flow ratio of the oligomer is output by the modifier masterbatch melt metering pump according to the oligomer delivery metering device After controlling the metering flow, it is directly injected into the feed pipe of the dynamic mixer.

The melt of oligomer and modifier polyhexamethylene adipamide masterbatch is uniformly mixed by a 3-stage high-shear dynamic mixer and then enters the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 270°C and the speed is 2500r/min, the aspect ratio of the vertical fully mixed flow reactor of the exchange reaction system is 1.8, the number of stirring paddles is 3 groups, the aspect ratio of the vertical plug flow reactor is 15, and the number of falling film unit layers is 30 The diameter of the vertical fully mixed flow reactor is 5 times that of the vertical plug flow reactor. Ethylene terephthalate/hexamethylene adipamide copolymer obtained by ester-amide exchange reaction of the melt blend of oligomer and modifier polyhexamethylene adipamide masterbatch in the exchange reaction system Finally, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the exchange reaction system has a reaction temperature of 265 ° C and a reaction time of 120 minutes.

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank, wherein the temperature of the reactants in the first pre-condensation tank is 265°C, and the temperature of the reactants in the second pre-condensation tank is 267°C. When the intrinsic viscosity of the prepolymer reaches 0.15dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 270°C. When the intrinsic viscosity of the final polymer reaches 0.78dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a hydrophilic polyester fiber: the breaking strength is 4.2cN/dtex, the breaking elongation is 32%, and the dyeing uniformity is grade 5. The dyeing results of the fiber show that the modifier polyhexamethylene adipamide molecular segment is evenly distributed in the main chain of the polyester molecule, so that the structure of the hydrophilic polyester is uniform, and the fiber dyeing has no color difference.

Example 8

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2808kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank for esterification For the reaction, the reaction temperature of the first esterification tank was 262°C, and the reaction temperature of the second esterification tank was 267°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 6, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from The second esterification tank is taken out.

The oligomer from the esterification reaction system is heated up to 300°C by a Sulzer type heat exchanger, and then enters the dynamic Mixer, the injection temperature of the polybutylene adipamide masterbatch melt is 300°C, the injection flow rate is 250kg/h, and the dynamic viscosity is 1000Pa.s. The process flow of polybutylene adipamide masterbatch injection is as follows : The polybutylene adipamide masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and the flow rate of the oligomer is output by the modifier masterbatch melt metering pump according to the oligomer delivery metering device The proportional control metering flow is directly injected into the feed pipe of the dynamic mixer.

The oligomer and modifier polybutylene adipamide masterbatch melt are uniformly mixed by a 4-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 300 °C and the speed is 2000r/min, the aspect ratio of the vertical fully mixed flow reactor of the exchange reaction system is 3, the number of stirring paddles is 4 groups, the aspect ratio of the vertical plug flow reactor is 10, and the number of falling film unit layers is 20 The diameter of the vertical fully mixed flow reactor is 2.5 times the diameter of the vertical plug flow reactor. Ethylene terephthalate/butylene adipamide copolymer obtained by ester-amide exchange reaction of the melt blend of oligomer and modifier polybutylene adipamide masterbatch in the exchange reaction system Finally, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the exchange reaction system has a reaction temperature of 295 ° C and a reaction time of 90 minutes.

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank. The temperature of the reactants in the first pre-condensation tank is 295°C, and the temperature of the reactants in the second pre-condensation tank is 300°C. When the intrinsic viscosity of the prepolymer reaches 0.20dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 300°C. When the intrinsic viscosity of the final polymer reaches 0.85dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a hydrophilic polyester fiber: the breaking strength is 3.8cN/dtex, the breaking elongation is 42%, and the dyeing uniformity is 4.5. The dyeing results of the fibers show that the polybutylene adipamide molecular segment of the modifying agent is evenly distributed in the main chain of the polyester molecule, so that the structure of the hydrophilic polyester is uniform, and the fiber dyeing has no color difference.

Example 9

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2808kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank for esterification For the reaction, the reaction temperature of the first esterification tank is 264°C, and the reaction temperature of the second esterification tank is 267°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 5, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from The second esterification tank is taken out.

The oligomer from the esterification reaction system is cooled to 250°C by a multi-tubular heat exchanger, and then enters the dynamic mixer together with the modifier polyethylene glycol solution from the modifier solution online injection device, and the polyethylene glycol solution The concentration is 90wt%, the injection temperature is 80°C, the injection flow rate is 300kg/h, and the dynamic viscosity is 5Pa.s. The technological process of polyethylene glycol solution injection is as follows: add polyethylene glycol to the modifier solution to prepare The tank is mixed with ethylene glycol to make a solution with a concentration of 90wt%, and then it is transferred to the modifier solution supply tank through the potential difference, and the metering is controlled by the modifier solution metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device After the flow is injected into the feed pipe of the dynamic mixer by the modifier solution injector.

The oligomer and modifying agent polyethylene glycol solution are uniformly mixed by a 2-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 230°C and the rotation speed is 3500r/min. The length-to-diameter ratio of the vertical full-mixed flow reactor of the system is 2, the number of stirring paddles is 4 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 5, and the number of falling film unit layers is 10 layers. The diameter of the reactor is 1.5 times that of the vertical plug flow reactor. After the blend of oligomer and modifier polyethylene glycol solution is obtained through transesterification reaction in the exchange reaction system to obtain ethylene terephthalate/polyethylene glycol copolymer, it is directly transported by the oligomer pump to The pre-condensation reaction system carries out the pre-condensation reaction, wherein the reaction temperature of the exchange reaction system is 250° C., and the reaction time is 45 minutes.

The pre-condensation reaction system consists of a vertical pre-condensation tank, wherein the temperature of the reactants in the pre-condensation tank is 275°C. When the prepolymer intrinsic viscosity reaches 0.30dL/g, the prepolymer pump is continuously and stably extracted from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 280°C. When the intrinsic viscosity of the final polymer reaches 0.90dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a hydrophilic polyester fiber: the breaking strength is 3.6cN/dtex, the breaking elongation is 35%, and the dyeing uniformity is 4.5. The dyeing results of the fiber show that the polyethylene glycol segment of the modifier is evenly distributed in the main chain of the polyester molecule, so that the structure of the hydrophilic polyester is uniform, and the fiber dyeing has no color difference.

Example 10

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2902kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank for esterification For the reaction, the reaction temperature of the first esterification tank is 260°C, and the reaction temperature of the second esterification tank is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 5, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from The second esterification tank is taken out.

The oligomer from the esterification reaction system is cooled to 255°C by a single-tube mixing heat exchanger, and then mixed with the flame retardant 2-carboxyethylphenyl phosphinic acid ethylene glycol ester solution from the modifier solution online injection device Enter dynamic mixer together, the concentration of ethylene glycol 2-carboxyethylphenyl phosphinate solution is 50wt%, and injection temperature is 60 ℃, injection flow rate is 490kg/h, dynamic viscosity is 1.5Pa.s, wherein 2 -The technical process of carboxyethylphenyl phosphinic acid ethylene glycol ester solution injection is: the 2-carboxyethyl phenyl phosphinic acid ethylene glycol ester esterification solution with an esterification rate of 85% is added to the modifier In the solution preparation tank, a solution with a concentration of 50wt% is prepared with ethylene glycol, and then it is transferred to the modifier solution supply tank through the potential difference, and the flow ratio of the oligomer is output by the modifier solution metering pump according to the oligomer delivery metering device After controlling the metering flow, inject the modifier solution injector into the feed pipe of the dynamic mixer.

The oligomer and modifying agent 2-carboxyethylphenylphosphinic acid ethylene glycol ester solution are uniformly mixed by a 5-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 230 ℃, rotating speed 50r/min, the length-to-diameter ratio of the vertical fully mixed flow reactor of the exchange reaction system is 0.5, the number of stirring paddles is 2 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 2, and the falling film unit layer The number is 4 layers, and the diameter of the vertical fully mixed flow reactor is 1.05 times the diameter of the vertical plug flow reactor. The solution blend of oligomer and modifying agent 2-carboxyethylphenyl phosphinate is obtained through transesterification reaction in the exchange reaction system to obtain ethylene terephthalate/2-carboxyethylbenzene After the base ethylene glycol phosphinate copolymer is directly transported by the oligomer pump to the precondensation reaction system for precondensation reaction, the reaction temperature of the exchange reaction system is 255°C and the reaction time is 10min.

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank, wherein the temperature of the reactants in the first pre-condensation tank is 265°C, and the temperature of the reactants in the second pre-condensation tank is 270°C. When the intrinsic viscosity of the prepolymer reaches 0.10dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank and a horizontal liquid phase thickening tank, wherein the reaction temperature of the final polycondensation tank is 275°C, and the reaction temperature of the liquid phase thickening tank is 280°C. When the intrinsic viscosity of the tackified final polymer reaches 0.75dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a flame-retardant polyester fiber: the breaking strength is 2.8cN/dtex, the breaking elongation is 25%, and the dyeing uniformity is 4.5 grades. The fiber dyeing results showed that the flame retardant 2-carboxyethylphenylphosphinate ethylene glycol ester segment was evenly distributed in the main chain of the polyester molecule, so that the structure of the flame retardant polyester was uniform, and the fiber dyeing had no color difference.

Example 11

The slurry formulated with terephthalic acid and butanediol is continuously and uniformly transported to the esterification tank consisting of a vertical first esterification tank and a horizontal second esterification tank with compartment structure at a flow rate of 2496kg/h. The esterification reaction is carried out in the reaction system, the reaction temperature of the first esterification tank is 230°C, and the reaction temperature of the second esterification tank is 240°C. A concentration of 3wt% esterification catalyst tetrabutyl titanate solution is continuously and uniformly injected into the first esterification kettle at a flow rate of 41.7kg/h; a concentration of 5wt% polycondensation catalyst tetrabutyl titanate and antimony acetate composite catalyst The solution is continuously and uniformly injected into the third compartment of the second esterification tank at a flow rate of 41.7kg/h. When the degree of polymerization of the esterified product butylene terephthalate oligomer reaches 1, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from Extracted from the esterification kettle.

The oligomer Sulzer type heat exchanger from the esterification reaction system is cooled to 180°C and enters the dynamic Mixer, the injection temperature of polybutylene succinate masterbatch melt is 160°C, the injection flow rate is 500kg/h, and the dynamic viscosity is 800Pa.s. The process of injecting polybutylene succinate masterbatch The process is: the polybutylene succinate masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and the oligomer is output through the modifier masterbatch melt metering pump according to the oligomer delivery metering device. The flow ratio of the material is used to control the metering flow and then directly injected into the feed pipe of the dynamic mixer.

The oligomer and modifier polybutylene succinate masterbatch melt are uniformly mixed by a 5-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 180°C and the speed is 3000r/min, the length-to-diameter ratio of the vertical fully mixed-flow reactor of the exchange reaction system is 2, the number of stirring paddles is 4 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 10, and the number of falling film unit layers is 30 layers, the diameter of the vertical fully mixed flow reactor is twice the diameter of the vertical plug flow reactor. The melt blend of oligomer and modifier polybutylene succinate masterbatch is obtained through transesterification reaction in the exchange reaction system to obtain butylene terephthalate/butylene succinate copolymer Finally, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the temperature of the exchange reaction system is 180 ° C, and the reaction time is 90 minutes.

The pre-condensation reaction system consists of a vertical pre-condensation tank, wherein the temperature of the reactants in the pre-condensation tank is 200°C. When the prepolymer intrinsic viscosity reaches 0.50dL/g, the prepolymer pump is continuously and stably extracted from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 200°C. When the intrinsic viscosity of the final polymer reaches 1.20dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a biodegradable polyester fiber: the breaking strength is 3.0cN/dtex, the breaking elongation is 45%, and the dyeing uniformity is grade 4. The results of fiber dyeing showed that the polybutylene succinate molecular segment of the modifier was evenly distributed in the main chain of the polyester molecule, so that the structure of the biodegradable polyester was uniform, and the fiber dyeing had no color difference.

Example 12

The slurry formulated with terephthalic acid and butanediol is continuously and evenly transported at a flow rate of 2328kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 230°C. The catalyst tetraisopropyl titanate solution with a concentration of 10 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 17.5 kg/h. When the degree of polymerization of the esterified butylene terephthalate oligomer reaches 2, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from Extracted from the esterification kettle.

The oligomer Sulzer type heat exchanger from the esterification reaction system is cooled to 200 °C and enters the dynamic Mixer, the injection temperature of polybutylene adipate masterbatch melt is 200°C, the injection flow rate is 750kg/h, and the dynamic viscosity is 5Pa.s. The process of injecting polybutylene adipate masterbatch The process is: the polybutylene adipate masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and the oligomer is output through the modifier masterbatch melt metering pump according to the oligomer delivery metering device. The flow ratio of the material is used to control the metering flow and then directly injected into the feed pipe of the dynamic mixer.

The oligomer and modifier polybutylene adipate masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 200°C and the speed is 4000r/min, the length-to-diameter ratio of the vertical fully mixed-flow reactor of the exchange reaction system is 3, the number of stirring paddles is 5 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 15, and the number of falling film unit layers is 40 layers, the diameter of the vertical fully mixed flow reactor is 5 times the diameter of the vertical plug flow reactor. Polybutylene terephthalate/butylene adipate copolymer is obtained by transesterification reaction of the melt blend of oligomer and modifier polybutylene adipate masterbatch in the exchange reaction system Finally, the oligomer pump is directly transported to the precondensation reaction system for precondensation reaction, wherein the temperature of the exchange reaction system is 200°C, and the reaction time is 120min.

The precondensation reaction system consists of a vertical precondensation tank, wherein the temperature of the reactants in the precondensation tank is 210°C. When the intrinsic viscosity of the prepolymer reaches 0.45dL/g, the prepolymer pump is continuously and stably withdrawn from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 220°C. When the intrinsic viscosity of the final polymer reaches 1.50dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a biodegradable polyester fiber: the breaking strength is 2.7cN/dtex, the breaking elongation is 50%, and the dyeing uniformity is 4.5. The results of fiber dyeing showed that the polybutylene adipate molecular segment of the modifier was evenly distributed in the main chain of the polyester molecule, so that the structure of the biodegradable polyester was uniform, and the fiber dyeing had no color difference.

Example 13

The slurry formulated with terephthalic acid and butanediol is continuously and evenly transported at a flow rate of 2993kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 230°C. The catalyst tetraisopropyl titanate solution with a concentration of 10 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 17.5 kg/h. When the degree of polymerization of the esterified butylene terephthalate oligomer reaches 3, the oligomer delivery and metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from Extracted from the esterification kettle.

The oligomer Sulzer type heat exchanger from the esterification reaction system is cooled to 200°C and enters the dynamic Mixer, the injection temperature of polyethylene adipate masterbatch melt is 180°C, the injection flow rate is 250kg/h, and the dynamic viscosity is 60Pa.s. The injection process of polyethylene adipate masterbatch The process is: the polyethylene adipate masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and the oligomer is output through the modifier masterbatch melt metering pump according to the oligomer delivery metering device. The flow ratio of the material is used to control the metering flow and then directly injected into the feed pipe of the dynamic mixer.

The melt of oligomer and modifier polyethylene adipate masterbatch is uniformly mixed by a 3-stage high-shear dynamic mixer and then enters the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 200°C and the speed is 2000r/min, the length-to-diameter ratio of the vertical fully mixed-flow reactor of the exchange reaction system is 2, the number of stirring paddle groups is 4, the length-to-diameter ratio of the vertical plug-flow reactor is 10, and the number of falling film unit layers is 25 layers, the diameter of the vertical fully mixed flow reactor is 3.5 times the diameter of the vertical plug flow reactor. The melt blend of oligomer and modifier polyethylene adipate masterbatch is obtained by transesterification reaction in the exchange reaction system to obtain butylene terephthalate/ethylene adipate oligomerization After the product, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the temperature of the exchange reaction system is 220 ° C, and the reaction time is 75 minutes.

The precondensation reaction system consists of a vertical precondensation tank, wherein the temperature of the reactants in the precondensation tank is 230°C. When the prepolymer intrinsic viscosity reaches 0.30dL/g, the prepolymer pump is continuously and stably extracted from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 240°C. When the intrinsic viscosity of the final polymer reaches 1.30dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a biodegradable polyester fiber: the breaking strength is 3.4cN/dtex, the breaking elongation is 28%, and the dyeing uniformity is grade 5. The result of fiber dyeing shows that the modifier polyethylene adipate molecular segment is evenly distributed in the main chain of polyester molecule, so that the structure of biodegradable polyester is uniform, and the fiber dyeing has no color difference.

Example 14

The slurry prepared by terephthalic acid and propylene glycol is continuously and uniformly transported at a flow rate of 3026kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank with compartment structure. For the esterification reaction, the reaction temperature of the first esterification tank is 225°C, and the reaction temperature of the second esterification tank is 235°C. Concentration is that the esterification catalyst ethylene glycol titanium solution of 3wt% is continuously and uniformly injected in the first esterification kettle with the flow rate of 41.6kg/h; Concentration is the polycondensation catalyst ethylene glycol antimony solution of 3wt% The flow rate is continuously and uniformly injected into the third compartment of the second esterification tank. When the degree of polymerization of the esterified product propylene glycol terephthalate oligomer reached 4, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter was continuously and stably flowed from the second Extracted from the esterification kettle.

The oligomer from the esterification reaction system is cooled to 220°C by a Sulzer type heat exchanger together with the modifier dipropylene glycol isophthalate-5-sodium sulfonate solution from the modifier solution online injection device into the dynamic mixer. The concentration of dipropylene glycol isophthalate-5-sodium sulfonate solution is 20wt%, the injection temperature is 110°C, the injection flow rate is 482kg/h, and the dynamic viscosity is 0.05Pa.s, wherein dipropylene glycol isophthalate- The technological process of injecting the 5-sodium sulfonate solution is as follows: adding the dipropylene glycol isophthalate-5-sodium sulfonate esterification liquid into the modifier solution preparation tank and preparing a solution with a concentration of 20 wt% with propylene glycol and then passing The potential difference is transferred to the modifier solution supply tank, and the metering flow is controlled by the modifier solution metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device, and then injected into the dynamic mixer feed pipe by the modifier solution injector.

The oligomer and modifying agent dipropylene glycol isophthalate-5-sodium sulfonate solution are uniformly mixed by a first-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 230°C , The rotating speed is 300r/min, the aspect ratio of the vertical fully mixed flow reactor of the exchange reaction system is 0.8, the number of stirring paddles is 2 groups, the aspect ratio of the vertical plug flow reactor is 4, and the falling film unit layer The number is 10 layers, and the diameter of the vertical fully mixed flow reactor is twice the diameter of the vertical plug flow reactor. , The blend of oligomer and modifier dipropylene glycol isophthalate-5-sodium sulfonate is obtained through transesterification reaction in the exchange reaction system to obtain propylene glycol terephthalate/dipropylene glycol isophthalate- After the 5-sodium sulfonate oligomer is produced, it is directly transported by the oligomer pump to the precondensation reaction system for precondensation reaction, wherein the reaction temperature of the exchange reaction system is 235° C., and the reaction time is 30 minutes.

The pre-condensation reaction system consists of a vertical pre-condensation tank, wherein the temperature of the reactants in the pre-condensation tank is 250°C. When the prepolymer intrinsic viscosity reaches 0.35dL/g, the prepolymer pump is continuously and stably extracted from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 260°C. When the intrinsic viscosity of the final polymer reaches 1.05dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a cationic dye-dyeable polyester fiber: the fiber breaking strength is 2.8cN/dtex, the breaking elongation is 38%, and the dyeing uniformity is grade 5. The dyeing results of the fibers showed that the modifying agent dipropylene glycol isophthalate-5-sodium sulfonate was evenly distributed in the main chain of the polyester molecule, so that the structure of the cationic dyeable polyester was uniform, and the fiber was dyed without color difference.

Example 15

The slurry formulated with terephthalic acid and cyclohexanedimethanol is continuously and uniformly transported to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank at a flow rate of 2496kg/h. The esterification reaction is carried out in the system, the reaction temperature of the first esterification tank is 270°C, and the reaction temperature of the second esterification tank is 280°C. The esterification catalyst antimony trioxide with a concentration of 3wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 25 kg/h. When the degree of polymerization of the cyclohexanedimethanol terephthalate oligomer of the esterified product reaches 6, the oligomer delivery metering device composed of an oligomer pump and an oligomer flow meter is continuously stable at a flow rate of 2080kg/h extracted from the esterification tank.

The oligomer from the esterification reaction system is cooled to 275°C by a single-tube mixing heat exchanger, and then together with the modifier polyethylene terephthalate masterbatch melt from the modifier masterbatch online injection device Entering the dynamic mixer, the injection temperature of polyethylene terephthalate masterbatch melt is 275°C, the injection flow rate is 500kg/h, and the dynamic viscosity is 300Pa.s, of which polyethylene terephthalate masterbatch The technological process of pellet injection is as follows: polyethylene terephthalate masterbatch is dried by the modifier masterbatch drying system, melted by the screw extruder, and passed through the modifier masterbatch melt metering pump according to the oligomer The flow ratio of the oligomer output by the conveying metering device is directly injected into the feed pipeline of the dynamic mixer after controlling the metering flow rate.

The melt of oligomer and modifier polyethylene terephthalate masterbatch is uniformly mixed by a 3-stage high-shear dynamic mixer and then enters the exchange reaction system for exchange reaction. The temperature of the dynamic mixer is 275°C, The rotation speed is 2500r/min, the length-to-diameter ratio of the vertical fully mixed flow reactor of the exchange reaction system is 3, the number of stirring paddles is 5 groups, the length-to-diameter ratio of the vertical plug-flow reactor is 8, and the number of falling film unit layers The diameter of the vertical full mixed flow reactor is 25 layers, and the diameter of the vertical plug flow reactor is 3 times that of the vertical plug flow reactor. The melt blend of oligomer and modifier polyethylene terephthalate masterbatch is obtained through transesterification reaction in the exchange reaction system to obtain cyclohexanedimethylene terephthalate/ethylene terephthalate After the alcohol ester oligomer is produced, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the reaction temperature of the exchange reaction system is 275° C., and the reaction time is 90 minutes.

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank. The temperature of the reactants in the first pre-condensation tank is 280°C, and the temperature of the reactants in the second pre-condensation tank is 285°C. When the intrinsic viscosity of the prepolymer reaches 0.25dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 290°C. When the intrinsic viscosity of the final polymer reaches 0.67dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a high-shrinkage polyester fiber: the breaking strength is 3.2cN/dtex, the breaking elongation is 45%, and the dyeing uniformity is grade 4. The dyeing results of the fiber show that the polyethylene terephthalate molecular segment of the modifying agent is evenly distributed in the main chain of the polyester molecule, so that the structure of the high-shrinkage polyester is uniform, and the fiber dyeing has no color difference.

Example 16

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2808kg/h to the esterification reaction system consisting of a vertical first esterification tank and a horizontal second esterification tank for esterification For the reaction, the reaction temperature of the first esterification tank is 260°C, and the reaction temperature of the second esterification tank is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the second esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 8, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from The second esterification tank is taken out.

The oligomer from the esterification reaction system is cooled to 230°C by a Sulzer type heat exchanger, and then mixed with the modifier diethylene glycol isophthalate-5-sodium sulfonate from the modifier solution online injection device The solution and the modifier polybutylene succinate masterbatch melt from the modifier masterbatch online injection device enter the dynamic mixer together, and the solution of diethylene glycol isophthalate-5-sodium sulfonate The concentration is 40wt%, the injection temperature is 80°C, the injection flow rate is 348kg/h, the dynamic viscosity is 0.6Pa.s, the injection temperature of the polybutylene succinate masterbatch melt is 160°C, and the injection flow rate is 250kg/h h. The dynamic viscosity is 800Pa.s. The technical process of injection of diethylene glycol isophthalate-5-sodium sulfonate solution is: add diethylene glycol isophthalate-5-sodium sulfonate esterification solution into the modifier solution preparation tank After being adjusted with ethylene glycol to form a solution with a concentration of 40wt%, it is transferred to the modifier solution supply tank through the potential difference, and the metering flow is controlled by the modifier solution metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device Inject the injector of the modifier solution into the feed pipe of the dynamic mixer; the technological process of polybutylene succinate masterbatch melt injection is as follows: the polybutylene succinate masterbatch passes through the modifier masterbatch drying system Dried, melted by a screw extruder, and directly injected into the feed pipe of the dynamic mixer through the modifier masterbatch melt metering pump to control the metering flow according to the flow ratio of the oligomer output from the oligomer delivery metering device.

The oligomer, diethylene glycol isophthalate-5-sodium sulfonate solution and polybutylene succinate masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then enter the exchange reaction system for further processing. Exchange reaction, in which the temperature of the dynamic mixer is 230°C, the speed is 1500r/min, the length-to-diameter ratio of the vertical fully mixed flow reactor of the exchange reaction system is 1, the number of stirring paddles is 2 groups, and the vertical plug flow reaction The aspect ratio of the kettle is 10, the number of falling film unit layers is 20, and the diameter of the vertical fully mixed flow reactor is 1.2 times the diameter of the vertical plug flow reactor. The melt blend of oligomer, diethylene glycol isophthalate-5-sodium sulfonate solution and polybutylene succinate master batch is obtained through transesterification reaction in the exchange reaction system to obtain terephthalic acid After ethylene glycol ester/butylene succinate/diethylene glycol isophthalate-5-sodium sulfonate ternary oligomer, the oligomer pump is directly transported to the pre-condensation reaction system for pre-condensation reaction, wherein the reaction temperature of the exchange reaction system is 235° C., and the reaction time is 60 minutes.

The pre-condensation reaction system consists of a vertical first pre-condensation tank and a horizontal second pre-condensation tank, wherein the temperature of the reactants in the first pre-condensation tank is 255°C, and the temperature of the reactants in the second pre-condensation tank is 265°C. When the intrinsic viscosity of the prepolymer reaches 0.20dL/g, the prepolymer pump is continuously and stably withdrawn from the second precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 275°C. When the intrinsic viscosity of the final polymer reaches 0.62dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is cationic dyeable polyester fiber under normal pressure: the fiber breaking strength is 3.4cN/dtex, the breaking elongation is 35%, and the dyeing uniformity is grade 5. The dyeing results of the fibers showed that the modifying agent ethylene glycol isophthalate-5-sodium sulfonate segment and polybutylene succinate segment were evenly distributed in the main chain of the polyester molecule, thus making the cationic dye often The structure of pressure-dyeable polyester is uniform, and its fiber dyeing has no color difference.

Example 17

The slurry formulated with terephthalic acid and ethylene glycol is continuously and uniformly transported at a flow rate of 2964kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 4, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably flowed from Extracted from the esterification kettle.

The oligomer from the esterification reaction system is cooled to 250°C by the Sulzer type heat exchanger, and then enters the dynamic mixer together with the modifier polycaprolactam masterbatch melt from the modifier masterbatch online injection device, and the polycaprolactam The injection temperature of the masterbatch melt is 250°C, the injection flow rate is 125kg/h, and the dynamic viscosity is 180Pa.s. The process flow of polycaprolactam masterbatch injection is as follows: the polycaprolactam masterbatch is dried by the modifier masterbatch drying system, It is melted by the screw extruder, and the metering flow is controlled by the modifier masterbatch melt metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device, and then directly injected into the feed pipe of the dynamic mixer.

The oligomer and modifier polycaprolactam masterbatch melts are evenly mixed by a 5-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The length-to-diameter ratio of the vertical fully mixed-flow reactor in the reaction system is 0.4, the number of stirring paddles is 1 group, the length-to-diameter ratio of the vertical plug-flow reactor is 30, and the number of falling film unit layers is 60. The diameter of the mixed flow reactor is 6 times that of the vertical plug flow reactor. After the melt blend of oligomer and modifier polycaprolactam masterbatch is obtained through ester-amide exchange reaction in the exchange reaction system to obtain ethylene terephthalate/caprolactam copolymer, it is directly transported by the oligomer pump to The precondensation reaction system carries out the precondensation reaction, wherein the reaction temperature of the exchange reaction system is 260° C., and the reaction time is 90 minutes.

The precondensation reaction system consists of a vertical polycondensation tank, and the reaction temperature of the precondensation tank is 270°C. When the prepolymer intrinsic viscosity reaches 0.30dL/g, the prepolymer pump is continuously and stably extracted from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 280°C. When the intrinsic viscosity of the final polymer reaches 0.80dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a hydrophilic polyester fiber: the breaking strength is 2.7cN/dtex, the breaking elongation is 23%, and the dyeing uniformity is 4.0 grade. The dyeing results of the fibers show that the modifier polycaprolactam molecular segments are evenly distributed in the main chain of the polyester molecule, so that the structure of the hydrophilic polyester is uniform, and the fiber dyeing has no color difference.

Example 18

The slurry formulated with terephthalic acid and ethylene glycol is continuously and uniformly transported at a flow rate of 2964kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 4, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably flowed from Extracted from the esterification kettle.

The oligomer from the esterification reaction system is cooled to 305°C by the Sulzer type heat exchanger, and then enters the dynamic mixer together with the modifier polycaprolactam masterbatch melt from the modifier masterbatch online injection device, and the polycaprolactam The injection temperature of the masterbatch melt is 250°C, the injection flow rate is 125kg/h, and the dynamic viscosity is 1100Pa.s. The process flow of polycaprolactam masterbatch injection is as follows: the polycaprolactam masterbatch is dried by the modifier masterbatch drying system, It is melted by the screw extruder, and the metering flow is controlled by the modifier masterbatch melt metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device, and then directly injected into the feed pipe of the dynamic mixer.

The oligomer and modifier polycaprolactam masterbatch melts are evenly mixed by a 5-stage high-shear dynamic mixer and then enter the exchange reaction system for exchange reaction. The length-to-diameter ratio of the vertical fully mixed-flow reactor in the reaction system is 0.4, the number of stirring paddles is 1 group, the length-to-diameter ratio of the vertical plug-flow reactor is 1.8, and the number of falling film unit layers is 3 layers. The diameter of the mixed-flow reactor is 1.02 times that of the vertical plug-flow reactor. After the melt blend of oligomer and modifier polycaprolactam masterbatch is obtained through ester-amide exchange reaction in the exchange reaction system to obtain ethylene terephthalate/caprolactam copolymer, it is directly transported by the oligomer pump to The precondensation reaction system carries out the precondensation reaction, wherein the reaction temperature of the exchange reaction system is 305° C., and the reaction time is 8 minutes.

The precondensation reaction system consists of a vertical polycondensation tank, and the reaction temperature of the precondensation tank is 270°C. When the intrinsic viscosity of the prepolymer reaches 0.09dL/g, the prepolymer pump is continuously and stably withdrawn from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 280°C. When the intrinsic viscosity of the final polymer reaches 0.48dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a hydrophilic polyester fiber: the breaking strength is 2.5 cN/dtex, the breaking elongation is 20%, and the dyeing uniformity is 4.0 grade. The dyeing results of the fibers show that the modifier polycaprolactam molecular segments are evenly distributed in the main chain of the polyester molecule, so that the structure of the hydrophilic polyester is uniform, and the fiber dyeing has no color difference.

Comparative example 1

The slurry formulated with terephthalic acid and ethylene glycol is continuously and evenly transported at a flow rate of 2964kg/h to the esterification reaction system consisting of vertical esterification tanks for esterification reaction, and the reaction temperature is 265°C. The catalyst ethylene glycol antimony solution with a concentration of 3 wt% was continuously and uniformly injected into the esterification tank at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 4, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably flowed from Extracted from the esterification kettle.

The oligomer from the esterification reaction system enters the precondensation reaction system together with the modifier polycaprolactam masterbatch melt from the modifier masterbatch online injection device for precondensation reaction. The injection temperature of the polycaprolactam masterbatch melt is 250°C, injection flow rate of 125kg/h, and dynamic viscosity of 180Pa.s. The process flow of polycaprolactam masterbatch injection is as follows: polycaprolactam masterbatch is dried by modifier masterbatch drying system, melted by screw extruder, passed through The modifier masterbatch melt metering pump is directly injected into the oligomer pipeline.

The precondensation reaction system consists of a vertical polycondensation tank, and the reaction temperature of the precondensation tank is 270°C. When the prepolymer intrinsic viscosity reaches 0.30dL/g, the prepolymer pump is continuously and stably extracted from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, and the reaction temperature of the final polycondensation tank is 280°C. When the intrinsic viscosity of the final polymer reaches 0.80dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is a hydrophilic polyester fiber: the breaking strength is 2.2cN/dtex, the breaking elongation is 15%, and the dyeing uniformity is grade 2. The dyeing results of the fibers showed that the modifier polycaprolactam molecular segments were not evenly distributed in the main chain of the polyester molecules, which made the structure of the hydrophilic polyester poor, and the color difference of the fiber dyeing appeared.

Comparative example 2

The slurry formulated with terephthalic acid and ethylene glycol is continuously and uniformly transported at a flow rate of 2964kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction, and the reaction temperature is 261°C. The catalyst antimony acetate solution with a concentration of 3.5wt% was continuously and evenly injected into the esterification kettle at a flow rate of 41.5kg/h. When the degree of polymerization of the esterified product ethylene terephthalate oligomer reaches 4, the oligomer delivery metering device composed of an oligomer pump and an oligomer flowmeter is continuously and stably transferred from Extracted from the esterification kettle.

The oligomer from the esterification reaction system enters the dynamic mixer together with the modifier diethylene glycol isophthalate-5-sodium sulfonate solution from the modifier solution online injection device. The concentration of diethylene glycol isophthalate-5-sodium sulfonate solution is 25wt%, the injection temperature is 90°C, the injection flow rate is 186kg/h, and the dynamic viscosity is 0.1Pa.s, wherein diethylene isophthalate The technological process of injection of glycol ester-5-sodium sulfonate solution is as follows: add diethylene glycol isophthalate-5-sodium sulfonate esterification solution into the modifier solution preparation tank and prepare it with ethylene glycol The solution with a concentration of 25wt% is then transferred to the modifier solution supply tank through the potential difference, and the metering flow is controlled by the modifier solution injector through the modifier solution metering pump according to the flow ratio of the oligomer output from the oligomer delivery metering device. Inject into the dynamic mixer feed line.

The oligomer and modifying agent diethylene glycol isophthalate-5-sodium sulfonate solution are uniformly mixed by a 3-stage high-shear dynamic mixer and then enter the pre-condensation reaction system for pre-condensation reaction. The temperature of the mixer is 230° C., and the rotation speed is 1000 r/min. The precondensation reaction system consists of a vertical precondensation reactor, wherein the temperature of the reactants in the precondensation reactor is 260° C. When the intrinsic viscosity of the prepolymer reaches 0.15dL/g, the prepolymer pump is continuously and stably withdrawn from the precondensation tank and transported to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation tank, wherein the reaction temperature of the final polycondensation tank is 275°C. When the intrinsic viscosity of the final polymer reaches 0.50dL/g, the modified polyester melt is directly transported to the spinning position through the melt pipeline for spinning to obtain the modified polyester fiber.

The fiber is cationic dyeable polyester fiber: the fiber breaking strength is 2.3cN/dtex, the breaking elongation is 18%, and the dyeing uniformity is 3.5. The dyeing results of the fiber show that the modifier diethylene glycol isophthalate-5-sodium sulfonate segment is unevenly distributed in the main chain of the polyester molecule, which makes the polyester structure uniformity dyeable by cationic dyes poor, and its fiber Color difference occurs in dyeing.

The modified polyester melt direct-spun fibers prepared in Examples 1 to 16 and Comparative Examples 1 to 2 are subjected to performance tests. The test items are as follows: breaking strength (cN/dtex), test method: refer to GB/T14344-2008 ; Elongation at break (%), test method: refer to GB/T14344-2008; Dyeing uniformity, test method: refer to GB/T6508-2001. The test results are shown in Table 1.

Breaking strength (cN/dtex) Elongation at break (%) Dyeing uniformity (level) Example 1 4.1 38 5.0 Example 2 3.0 32 4.5 Example 3 4.2 45 4.5 Example 4 4.8 25 4.0 Example 5 6.0 twenty four 4.0 Example 6 3.2 50 4.5 Example 7 4.2 32 5.0 Example 8 3.8 42 4.5 Example 9 3.6 35 4.5 Example 10 2.8 25 4.5 Example 11 3.0 4.5 4.0 Example 12 2.7 50 4.5 Example 13 3.4 28 5.0 Example 14 2.8 38 5.0 Example 15 3.2 45 4.0 Example 16 3.4 35 5.0 Example 17 2.7 twenty three 4.0 Example 18 2.5 20 4.0 Comparative example 1 2.2 15 2.0 Comparative example 2 2.3 18 3.5

As can be seen from the data in Table 1, the breaking strength of the modified polyester melt direct spinning fiber prepared by the modified polyester production method of the present invention is 2.5～6.0cN/dtex, and the breaking elongation is 20～50% , the dyeing uniformity is 4-5 grades, not only the breaking strength and breaking elongation of the fiber can meet the requirements of subsequent weaving, but also has a higher dyeing uniformity than the modified polyester fiber prepared by the existing technology, indicating that The modified polyester fiber prepared by the modified polyester production method of the present invention has higher structural uniformity.

In order to further illustrate the beneficial effects of the modified polyester production method of the present invention, differential scanning calorimetry was used to analyze and compare the thermal properties of the modified polyester fibers obtained in Example 1 of the present invention and Comparative Example 1. Test method: Using the Pyris1 differential scanning calorimeter of Perkin Elmer, the sample was first heated up to 280°C and kept at a constant temperature for 5 minutes to completely eliminate the thermal history, then the sample was quenched in liquid nitrogen, and then the sample was cooled from 30°C The temperature was raised to 280°C at a rate of 20°C/min. Fig. 4 is the DSC scanning curve of modified polyester, wherein a graph is the DSC temperature rising curve of the modified polyester prepared in Example 1, and b graph is the DSC temperature rising curve of the modified polyester prepared in Comparative Example 1.

It can be seen from Fig. 4 that there is only one melting peak on the DSC heating curve of the modified polyester prepared in Example 1, and its peak value is 233.3° C., while two melting peaks appear on the DSC heating curve of the modified polyester prepared in Comparative Example 1. There are two melting peaks, and their peaks are respectively 203.6°C and 248.9°C, which shows that the modifier polycaprolactam segments in the modified polyester prepared in Example 1 are evenly distributed in the main chain of the polyester molecule, forming a uniform structure. Polyester-polycaprolactam block copolymers. However, the modifier polycaprolactam in the modified polyester prepared in Comparative Example 1 exists in the form of a blend or in the form of long chain segments embedded in the polyester molecular chain, resulting in poor structural uniformity of the modified polyester.

Embodiment 1 of the present invention and comparative example 1 prepare the raw material formulation that modified polyester adopts, esterification reaction condition and polycondensation reaction condition are all the same, the difference of two kinds of preparation methods is that embodiment 1 is in the preparation of modified polyester In the process, a dynamic mixer mixing process and an exchange reaction process are introduced. The high-efficiency dispersion of the modifier polycaprolactam in the polyester oligomer is achieved through the dynamic mixer mixing process, so that the subsequent exchange reaction between the modifier polycaprolactam and the polyester oligomer is close to a homogeneous reaction; through the exchange In the reaction process, the modifying agent polycaprolactam is introduced into the main chain of the polyester oligomer molecule through an exchange reaction to obtain a polyester-polycaprolactam oligomer with a uniform structure, thereby ensuring the uniformity of the modified polyester structure of the final polycondensation product . In addition, it can also be seen from Table 1 that the breaking strength, elongation at break and dyeing uniformity of the modified polyester fiber obtained in Example 1 of the present invention are significantly better than those of the modified polyester fiber obtained in Comparative Example 1.

In order to specifically illustrate the beneficial effects of the exchange reaction process in the modified polyester production method provided by the present invention, the properties of the modified polyester fibers obtained in Example 2 of the present invention and Comparative Example 2 were analyzed and compared. The raw material formulations, esterification reaction conditions, polycondensation reaction conditions and dynamic mixing conditions used to prepare modified polyester in Example 2 of the present invention and Comparative Example 2 are all the same. The exchange reaction process is introduced in the process of permanent polyester. The uniform distribution of modifier diethylene glycol isophthalate-5-sodium sulfonate in the main chain of polyester molecules has been realized by the exchange reaction process, which solves the problems caused by modifier m-benzene in the production method of the prior art. The self-polymerization of diethylene glycol dicarboxylate-5-sodium sulfonate causes its inhomogeneous distribution in the main chain of polyester molecules. It can also be seen from Table 1 that the breaking strength, elongation at break and dyeing uniformity of the modified polyester fiber obtained in Example 2 of the present invention are significantly better than those of the modified polyester fiber obtained in Comparative Example 2.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (21)

1. an exchange reaction system, is characterized in that, described exchange reaction system comprises:

Vertical complete mixing flow reactor (2), comprises the first material inlet (1) disposed thereon and the first material outlet;

Vertical laminar flow reactor (7), comprises the second material inlet disposed thereon and the second material outlet (10);

Wherein, described vertical complete mixing flow reactor (2) is arranged on the roof of described vertical laminar flow reactor (7), and described first material outlet is connected with described second material inlet.

2. exchange reaction system according to claim 1, it is characterized in that, the diapire of described vertical complete mixing flow reactor (2) and the roof of described vertical laminar flow reactor (7) share at least partly, formed and share still wall, described first material outlet and described second material inlet overlap, and be arranged on described shared still wall.

3. exchange reaction system according to claim 2, is characterized in that, described shared still wall has the structure of the relatively described vertical complete mixing flow reactor (2) in middle part to lower recess.

4. exchange reaction system according to claim 1, it is characterized in that, described vertical complete mixing flow reactor (2) and described vertical laminar flow reactor (7) are coaxially arranged, preferably described first material outlet and described second material inlet overlapping and be positioned on the axis of described vertical complete mixing flow reactor (2) and described vertical laminar flow reactor (7).

5. exchange reaction system according to claim 1, it is characterized in that, the draw ratio of described vertical complete mixing flow reactor (2) is 0.5 ~ ~ 3, the draw ratio of described vertical laminar flow reactor (7) is 2 ~ 20, and the diameter of described vertical complete mixing flow reactor (2) is greater than the diameter of described vertical laminar flow reactor (7); More preferably the diameter of described vertical complete mixing flow reactor (2) is 1.05 ~ 5 times of described vertical laminar flow reactor (7) diameter.

6. exchange reaction system according to claim 1, is characterized in that, described exchange reaction system further comprises liquid level cascade control system, and described liquid level cascade control system comprises:

Fluid level transmitter, for sensing described vertical complete mixing flow reactor (2) internal liquid level height, and sends liquid level signal according to described liquid level information;

Electric control valve, be arranged on the connecting pipeline of the first material outlet of described vertical complete mixing flow reactor (2) and the first material inlet of described vertical laminar flow reactor (7), for receiving described liquid level signal, and according to described liquid level Signal Regulation motorized adjustment valve opening.

7. exchange reaction system according to claim 1, is characterized in that, described vertical complete mixing flow reactor (2) comprises the first kettle and agitator, and described agitator comprises:

Puddler (5), is connected on described first kettle, and one end extends to described first kettle inside;

Multiple paddle (6), is arranged on described puddler (5) axial symmetry or radiation symmetric;

Preferred described agitator comprises the many groups of paddle groups along described puddler (5) bearing of trend parallel arrangement, each described paddle group comprises the multiple described paddle (6) be arranged in same level, more preferably the group number of described paddle group is 2 ~ 5 groups, and more preferably in two adjacent groups paddle group, each paddle (6) is staggered.

8. exchange reaction system according to claim 7, it is characterized in that, heating inner coil pipe assembly (3) is also comprised in described vertical complete mixing flow reactor (2), described heating inner coil pipe assembly (3) is arranged in described first kettle, and arranges around described agitator; Preferred described heating inner coil pipe assembly (3) comprises arranging how group heats inner coil pipe with concentric circular fashion, and each described heating inner coil pipe is arranged along the axial screw of described vertical complete mixing flow reactor (2).

9. exchange reaction system according to claim 1, it is characterized in that, described vertical laminar flow reactor (7) comprises the second kettle and is arranged on the falling liquid film assembly in described second kettle, and described falling liquid film assembly comprises the falling liquid film unit (12) that multilayer parallel is arranged; Preferred described falling liquid film assembly comprises 4 ~ 40 layers of described falling liquid film unit (12).

10. exchange reaction system according to claim 9, is characterized in that, described falling liquid film unit comprises:

Perforated decking (8);

Overflow tower tray (9), is arranged on the downstream of described Perforated decking (8) along Flow of Goods and Materials direction, and described overflow tower tray (9) is provided with overfall;

Preferably, described Perforated decking (8) has the structure of center towards projection, and the overfall of described overflow tower tray (9) is positioned at the center of described overflow tower tray (9), more preferably described Perforated decking (8) is cone parachute plate.

11. 1 kinds of modified poly ester production systems, comprise esterification system, precondensation system and final minification and gather system, it is characterized in that, described modified poly ester production system also comprises and is arranged at the online add-on system of modifier between described esterification system and described precondensation system and the exchange reaction system according to any one of claim 1 to 10 according to Flow of Goods and Materials order.

12. modified poly ester production systems according to claim 11, is characterized in that, the online add-on system of described modifier comprises modifier master batch online injection device and/or modifier solution online injection device; Preferably

Described modifier master batch online injection device comprises the modifier master batch drying system, screw extruder, the modifier master batch melt metering pump that connect successively;

Described modifier solution online injection device comprises the modifier solution modulation tank, modifier solution charging-tank, modifier solution measuring pump and the modifier solution syringe that connect successively.

13. modified poly ester production systems according to claim 12, is characterized in that, described modified poly ester production system also comprises the dynamic mixer be arranged between the online add-on system of described modifier and described exchange reaction system; Preferred described dynamic mixer is 1 ~ 5 grade of high shear dynamic mixer.

14. modified poly ester production systems according to claim 12, it is characterized in that, described modified poly ester production system also comprises and is arranged at oligomer heat exchanger between described esterification system and described online add-on system and oligomer metering device by stream flow order, the oligomer flowmeter after preferred described oligomer transport metering mechanism comprises oligomer pump and is arranged on oligomer pump.

The preparation method of 15. 1 kinds of modified poly esters, is characterized in that, described preparation method comprises the following steps:

Prepare slurry and modifier respectively;

Described slurry is added the modified poly ester production system according to any one of claim 11 to 14, described modifier is added the online add-on system of the modified poly ester production system according to any one of claim 11 to 14, to obtain described modified poly ester.

16. preparation methods according to claim 15, is characterized in that, prepare in the process of described modifier and prepare the modifier that dynamic viscosity is 0.05Pa.s ~ 1000Pa.s.

17. preparation methods according to claim 16, is characterized in that,

When described modified poly ester production system comprises described oligomer heat exchanger, described oligomer temperature is adjusted to 180 ~ 300 DEG C by described oligomer heat exchanger;

When described modified poly ester production system comprises described dynamic mixer, the rotating speed of described dynamic mixer is 50 ~ 5000r/min.

18. preparation methods according to claim 17, is characterized in that, the reaction temperature of described exchange reaction system is 180 ~ 300 DEG C, and the reaction time is 10 ~ 180min.

19. preparation methods according to claim 18, is characterized in that, the on-line checkingi viscosity of the pre-polymer melt obtained after described precondensation system is 0.10 ~ 0.50dL/g; The on-line checkingi viscosity of the whole polymer melt obtained after gathering system preferably through described final minification is 0.50 ~ 1.50dL/g.

20. 1 kinds of modified polyester fiber products, is characterized in that, the modified polyester fiber that the modified polyester fiber production system of described modified polyester fiber product according to any one of claim 11 to 14 is produced is prepared from.

21. modified polyester fiber products according to claim 20, is characterized in that, the fracture strength of described modified polyester fiber product is 2.5 ~ 6.0cN/dtex, and elongation at break is 20 ~ 50%, and dye uniformity is 4 ~ 5 grades.