WO2016045020A1

WO2016045020A1 - Exchange reaction system, modified polyester production system comprising same, modified polyester production method and modified polyester fibre product

Info

Publication number: WO2016045020A1
Application number: PCT/CN2014/087360
Authority: WO
Inventors: 李鑫; 邱志成; 金剑; 孔令熙; 汪少朋; 吴一平; 刘锦阳
Original assignee: 中国纺织科学研究院
Priority date: 2014-09-24
Filing date: 2014-09-24
Publication date: 2016-03-31
Also published as: RU2666863C1

Abstract

Provided are an exchange reaction system, a modified polyester production system comprising same, a modified polyester production method and a modified polyester fibre product. The exchange reaction system comprises a vertical complete mixed flow reaction kettle and a vertical plug flow reaction kettle. The vertical complete mixed flow reaction kettle comprises a first material inlet and a first material outlet provided thereon; and the vertical plug flow reaction kettle comprises a second material inlet and a second material outlet provided thereon, wherein the vertical complete mixed flow reaction kettle is provided on the top wall of the vertical plug flow reaction kettle, and the first material outlet is in communication with the second material inlet. The exchange reaction system of such a directly connected structure can allow a material to quickly and conveniently enter the vertical plug flow reaction kettle under the action of gravity such that the exchange reaction conditions are close to a homogeneous phase, which thus improves the distribution uniformity of a modifier in the backbone of polyester molecules, and thereby the obtained modified polyester structure is highly uniform, and the system is suitable for producing high quality fibre and film products.

Description

Exchange reaction system, modified polyester production system containing the same, modified polyester production method and modified polyester fiber product

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 same, a modified polyester production method and a modified polyester fiber product.

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 advancement and market demand, the global polyester industry has experienced rapid development in recent years, and product homogenization competition has become increasingly fierce. Facing the new competitive situation and severe environment at home and abroad, facing the current situation of severe overcapacity of conventional varieties, actively exploring the road of sustainable development of the industry, accelerating the transformation and upgrading of polyester products and technologies is the key; developing the production of differentiated polyester products Process and equipment are the main ways to achieve transformation and upgrading.

The technical approaches for developing 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, and physical modification is to uniformly mix the functional modifier with the polyester matrix to form a blend, thereby imparting moisture absorption and resistance to the polyester. Physical properties such as flammable, antibacterial, conductive or cationic dyes. The efficient dispersion of the modifier and the precise control of the proportion of addition are key to ensuring the stability of the differentiated polyester production and the uniformity of the product structure.

At present, before the polycondensation process, the mixing and dispersing of the modifier in the main material is mainly the agitator of the esterification kettle and the static mixer of the oligomer pipeline. Both of these equipments cannot crush and homogenize the materials, which is difficult to achieve. The uniform mixing between the main material and the incompatible modifier ultimately leads to poor homogeneity of the modified polyester structure, and the dyed fiber is liable to cause chromatic aberration when dyed. Therefore, how to improve the uniformity of the modified polyester structure has become an urgent problem to be solved.

Summary of the invention

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

In order to achieve the above object, according to an aspect of the present invention, an exchange reaction system comprising: a vertical full mixed flow reactor and a vertical flat flow reactor, a vertical full mixed flow reactor, including a first material inlet and a first material outlet disposed thereon; a vertical flat flow reactor comprising a second material inlet and a second material outlet disposed thereon; wherein the vertical full mixed reactor is set up The flat material is pushed on the top wall of the reaction vessel, and the first material outlet is in communication with the second material inlet.

Further, the bottom wall of the vertical full mixed reaction reactor is at least partially shared with the top wall of the vertical flat flow reaction reactor to form a common kettle wall, and the first material outlet and the second material inlet are overlapped and disposed on the common kettle wall. .

Further, the common kettle wall has a structure in which the central opposite vertical full mixed reaction reactor is recessed downward.

Further, the vertical full mixed flow reactor and the vertical flat flow reaction kettle are arranged coaxially, preferably the first material outlet and the second material inlet overlap and are located in the axis of the vertical full mixed reaction reactor and the vertical flat flow reactor on.

Further, the vertical full-flow reactor has an aspect ratio of 0.5 to 3, the vertical flat flow reactor has a length to diameter ratio of 2 to 20, and the vertical full mixed reactor has a larger diameter than the vertical flat flow reactor. The diameter of the vertical full-flow reactor is more preferably 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 comprises: a liquid level transmitter for sensing the liquid level inside the vertical full mixed reaction reactor, and according to the liquid level height The information sending liquid level height signal; the electric regulating valve is disposed on the communication line between the first material outlet of the vertical full mixed reaction kettle and the first material inlet of the vertical flat flow reaction kettle, for receiving the liquid level height signal, The electric control valve opening degree is adjusted according to the liquid level height signal.

Further, the vertical full mixed reaction reactor comprises a first kettle body and a stirrer, the stirrer comprises: a stirring rod connected to the first kettle body and one end extending to the inside of the first kettle body; a plurality of stirring blades, axisymmetric Or the radiation is symmetrically disposed on the stirring rod; preferably, the agitator comprises a plurality of sets of stirring paddles arranged in parallel along the extending direction of the stirring rod, each stirring paddle group comprises a plurality of stirring paddles disposed on the same horizontal surface, more preferably a stirring paddle group The number of groups is 2 to 5 groups, and it is more preferable that the stirring blades in the adjacent two groups of stirring paddles are alternately arranged.

Further, the vertical full mixed flow reactor further comprises a heating inner coil assembly, the heating inner coil assembly is disposed in the first kettle body and disposed around the agitator; preferably heating the inner coil assembly comprises setting the plurality of groups in a concentric manner The inner coil is heated, and each heated inner coil is spirally disposed along the axial direction of the vertical full mixed reaction reactor.

Further, the vertical plug flow reactor comprises a second kettle body and a falling film assembly disposed in the second kettle body, the falling film assembly comprising a plurality of falling film falling units arranged in parallel; preferably the falling film assembly comprises 4 to 40 layers Falling film unit.

Further, the falling film unit comprises: a porous cover plate; an overflow tray disposed 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 upward The raised structure, and the overflow of the overflow tray is located at the center of the overflow tray, and more preferably the perforated cover is a conical umbrella.

According to another aspect of the present invention, there is also provided a modified polyester production system comprising an esterification system, a precondensation system and a final polycondensation system, the modified polyester production system further comprising an esterification system in accordance with a material flow sequence A modifier online addition system between the precondensation system and any of the above exchange reaction systems.

Further, the modifier online addition system comprises a modifier masterbatch in-line injection device and/or a modifier solution in-line injection device; preferably, the modifier masterbatch on-line injection device comprises a modifier masterbatch drying system sequentially connected, Screw extruder, modifier masterbatch melt metering pump; modifier solution in-line injection device includes modifier solution solution tank, modifier solution supply tank, modifier solution metering pump and modifier Solution syringe.

Further, the modified polyester production system further includes a dynamic mixer disposed between the modifier online addition system and the exchange reaction system; preferably, the dynamic mixer is a 1 to 5 high shear dynamic mixer.

Further, the modified polyester production system further comprises an oligomer heat exchanger and an oligomer metering device disposed between the esterification system and the on-line addition system in a flow sequence, preferably the oligomer transport metering device comprises oligomerization The material pump and the oligomer flow meter disposed behind the oligomer pump.

According to still another aspect of the present invention, there is provided a method for preparing a modified polyester, which comprises the steps of separately preparing a slurry and a modifier; and adding the slurry to any of the above modified polyester production systems. The modifier is added to the in-line addition system of any of the above modified polyester production systems to obtain a modified polyester.

Further, a modifier having a kinetic viscosity of 0.05 Pa.s to 1000 Pa.s is prepared during the preparation of the modifier.

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

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

Further, the in-line viscosity of the prepolymer melt obtained after passing through the precondensation system is 0.10 to 0.50 dL/g, and the on-line viscosity of the final polymer melt obtained after the final polycondensation system is 0.50 to 1.50 dL/g. .

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

Further, the modified polyester fiber product has a breaking strength of 2.5 to 6.0 cN/dtex, an elongation at break of 20 to 50%, and a dyeing uniformity of 4 to 5.

By applying the technical scheme of the present invention, the material is highly efficient in the vertical full-flow reactor by placing the vertical full-mix reactor in the direct-connected exchange reaction system on the top wall of the vertical plug flow reactor. Mix After the state, it can quickly and conveniently enter the vertical flat flow reactor under the action of gravity, which greatly shortens the time from the vertical full mixed flow reactor to the vertical flat flow reaction kettle, so that the material is in the vertical stage. The near-homogeneous exchange reaction state in the full mixed-flow reactor can be transferred to the vertical plug flow reactor in a relatively short period of time for subsequent near-homogeneous exchange reaction, so that the conditions of the exchange reaction can be easily controlled and can be improved. The uniformity of the distribution of the modifier in the polyester molecular backbone makes the obtained modified polyester structure highly uniform and suitable for the production of high quality fiber and film products.

DRAWINGS

The accompanying drawings, which are incorporated in the claims of the claims In the drawing:

Figure 1 shows an exchange reaction system provided in accordance with an exemplary embodiment of the present invention;

2 shows a process flow of a modified polyester production system provided in accordance with an exemplary embodiment of the present invention;

Figure 3 illustrates a modified polyester production system provided in accordance with an exemplary embodiment of the present invention;

4 shows DSC scan curves of modified polyesters prepared according to Example 1 and Comparative Example 1 of the present invention.

detailed description

It should be noted that the embodiments in the present application and the features in the embodiments may be combined with each other without conflict. The invention will be described in detail below with reference to the drawings in conjunction with the embodiments.

As mentioned in the background art, in the prior art, there is a technical problem that it is difficult for the incompatible modifier to be uniformly mixed with the main material to cause poor uniformity of the modified polyester structure. In order to improve the above-mentioned drawbacks of the prior art, the present invention provides an exchange reaction system, as shown in FIG. 1, the exchange reaction system comprises: a vertical full mixed flow reactor 2 and a vertical flat flow reactor 7, vertical The full mixed-flow reactor 2 includes a first material inlet and a first material outlet disposed thereon; the vertical flat-flow reactor 7 includes a second material inlet and a second material outlet disposed thereon; wherein, the vertical full The mixed flow reaction kettle is disposed on the top wall of the vertical flat flow reaction kettle, and the first material outlet is in communication with the second material inlet.

In the above exchange reaction system of the present invention, the material is arranged in the vertical full mixed reaction reactor by placing the vertical full mixed reaction reactor on the top of the vertical flat flow reactor on the top of the exchange reaction system of the direct connection structure. After high-efficiency mixing, it can quickly and conveniently enter the vertical push-flow reactor under the action of gravity, which greatly shortens the time from the vertical full-flow reactor to the vertical flat-flow reactor, so that the material is in the early stage. Vertical full mixed flow The near-uniform exchange reaction state in the reactor can be transferred to the vertical plug flow reactor in a relatively short period of time for subsequent near-homogeneous exchange reaction, so that the conditions of the exchange reaction can be easily controlled, and the polyester can be improved. The uniformity of the distribution of the modifier in the molecular backbone makes the obtained modified polyester structure highly uniform and suitable for the production of high quality fiber and film products.

In the above exchange reaction system of the present invention, the direct connection of the two reactors is realized by arranging the vertical full mixed reaction reactor 2 on the top wall of the plug flow reactor. The reaction conditions of such a directly linked exchange reaction system are easily controlled compared to the two reactors connected by a pipe. In order to further optimize the above structure, the vertical full mixed flow reactor may be shared with the top wall portion of the vertical plug flow reactor to form a common wall, and the first material outlet and the second material inlet overlap each other and are disposed in the common On the wall. The one-piece exchange reaction system not only reduces the production cost, but also shortens the flow period between the vertical full-flow reactor and the vertical flat-flow reactor, so that the material can be quickly integrated into the vertical level after being uniformly mixed. The reactor is pushed into the reaction vessel to further achieve uniformity of distribution of the modifier in the main chain of the polyester molecule.

In the above exchange reaction system of the present invention, the common wall of the vertical full mixed flow reaction kettle and the vertical flat flow reaction reactor has a structure in which the central opposite vertical full mixed flow reactor is recessed downward, and the downwardly recessed structure is convenient. The materials are relatively gently flowed from the first material outlet into the flat flow reactor to maintain the relative uniformity of the materials.

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

Considering the optimization effect of the mixing degree and residence time of the materials on the exchange reaction, in the above-mentioned exchange reaction system of the present invention, it is preferable that the vertical full-flow reaction reactor 2 has an aspect ratio of 0.5 to 3, and the vertical flat flow reaction reactor stands. The aspect ratio reactor 7 has an aspect ratio of 2 to 20, and the vertical full mixed flow reactor 2 has a larger diameter than the vertical plug flow reactor 7; more preferably the diameter of the vertical full mixed reactor 2 It is 1.05 to 5 times the diameter of the vertical flat flow reactor 7 . When the aspect ratio of the vertical full-flow reactor is within the above range, the mixing of the materials in each place is more uniform, and there is no dead angle; the vertical flat-flow reactor with the aspect ratio within the above range has a small diameter and a high diameter. The tower structure of the aspect ratio can increase the difference and facilitate the flow of material from top to bottom in the reactor by its own gravity.

On the basis of the above, the diameter of the vertical full mixed reaction reactor 2 is larger than the diameter of the vertical flat flow reactor 7; more preferably, when the diameter of the vertical full mixed reactor 2 is the diameter of the vertical flat flow reactor From 1.05 to 5 times, it can not only utilize the large diameter and low aspect ratio of the vertical full mixed reaction reactor, but also facilitate the more uniform mixing of materials in various places, and has no advantage of dead angle. It also integrates the flat flow reactor with small diameter and high diameter. The tower structure of the aspect ratio can increase the difference, and realizes the beneficial effect of facilitating the flow of the material from top to bottom in the reactor by its own gravity, and saves the floor space of the reaction system.

In order to make the material more fully mixed in the vertical full mixed flow reactor, in a preferred embodiment of the invention, the exchange reaction system further comprises a liquid level cascade control system, the liquid level cascade control system comprising liquid Position transmitter and electric regulating valve, liquid level transmitter, used to sense the internal liquid level of the vertical full mixed flow reactor, and send the liquid level height signal according to the liquid level height information; electric regulating valve, set in vertical The first material outlet of the full mixed flow reaction kettle is connected with the first material inlet of the flat flow reaction kettle for receiving the liquid level height signal, and adjusting the opening degree of the electric regulating valve according to the liquid level height signal. By using the above liquid level transmitter to sense the liquid level of the material in the vertical full 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 liquid level in the vertical full-flow reactor, that is, the liquid level, is required to form a homogeneous fluid by exchange reaction of a blend of a modifier and a polyester oligomer. Stay time to determine. In actual production, the liquid level in the vertical full-flow reactor can be reasonably adjusted according to the required residence time.

In the above exchange reaction system of the present invention, the vertical full mixed flow reactor is mainly for achieving full mixed flow mixing of materials, and therefore, a vertical full mixed flow reactor capable of achieving the above functions is suitable for use in the present invention. In the present invention, the vertical full mixed flow reactor comprises a first kettle body and a stirrer, and the stirrer stirs the materials to achieve efficient and uniform mixing of the materials. In the present invention, the agitator used includes a stirring rod 5 and a plurality of stirring rods 6, which are 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 The radiation is symmetrically arranged on the stirring rod 5. The stirring rod 5 is attached to the first body and is driven by a motor disposed outside the first body.

Depending on the magnitude of the required agitation, a plurality of agitating rods 6 are preferably arranged axially symmetrically or radially symmetrically on the agitating rod 5 to achieve uniform agitation and efficient uniform mixing of the material in the first kettle body. The stirring rod 6 provided in the above manner of the invention has strong stirring action, and can uniformly disperse the modifier in the material in the micro-scale form in the polyester oligomer, thereby making the polyester oligomer and the modifier The exchange reaction between the two is close to the homogeneous reaction, which increases the exchange reaction rate and shortens the reaction time, which effectively restricts the occurrence of side reactions such as thermal degradation of the modifier.

In the above preferred embodiment, it is further preferred that the agitator comprises a plurality of sets of agitating paddles arranged in parallel along the extending direction of the stirring rod 5, each of the agitating paddles comprising a plurality of stirring bars 6 disposed on the same horizontal surface to achieve different A uniform mixing of the material at the level of the liquid level and the material at the same level. In actual production, the number of sets of the above-mentioned stirring paddles can be appropriately adjusted according to the amount of the material to be processed normally. In the present invention, it is preferable that the number of sets of the stirring paddle is 2 to 5. More preferably, each of the stirring rods 6 in the adjacent two groups of stirring paddles is staggered, so that the flow of materials passing through different adjacent groups of the stirring paddles is relatively lengthened, so that the mixing 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 device inside the vertical full mixed flow reactor, as long as the reaction temperature required for the material can be satisfied. In a preferred embodiment of the present invention, the vertical full mixed flow reactor further comprises a heated inner coil assembly, the heated inner coil assembly being disposed in the first kettle body and disposed around the agitator. The heated inner disk assembly is disposed around the agitator to maintain a relatively uniform temperature of the material while stirring and mixing to achieve uniformity of mixing, thereby bringing the early exchange reaction to a near homogeneous reaction state.

In the above embodiment, it is further preferred that the heating the inner coil assembly comprises disposing a plurality of sets of heated inner coils in a concentric manner, each of the heated inner coils being disposed in an axial spiral along the vertical full mixed flow reactor. This arrangement allows the material to be more evenly heated in the radial and axial directions. The above-mentioned heating inner coil of the invention adopts an independent secondary heat medium system, and the temperature of the heat medium in the heating coil can be adjusted to quickly adjust the temperature of the reaction material of the reaction system, thereby effectively restricting the occurrence of thermal degradation side reaction of the modifier. .

In the above-mentioned exchange reaction system of the present invention, the plug flow reactor can be a flat push flow reactor which is commonly used in the art, as long as it can achieve a flat push flow mixing effect on the material. In a preferred embodiment of the present invention, the plug flow reactor comprises a second kettle body and a falling film assembly disposed in the second body, and the falling film assembly comprises a plurality of falling film falling units 12 disposed in parallel.

By providing the multi-layer falling film unit 12 in the second kettle body, the homogeneous fluid formed by the preliminary exchange reaction can enter the lower push-flow reactor under the pressure difference, and then pass through the self-gravity. The falling film assembly composed of the layer falling film unit 12 flows downward in a flat pushing manner, and this flow mode can realize the first in first out of the reaction material. Therefore, the degree of exchange reaction can be effectively controlled by adjusting the reaction temperature and residence time of the material in the plug flow reactor, and a modified polyester oligomer having uniform structure can be obtained.

In the above embodiment of the invention, the residence time of the reactant stream material is adjusted by adjusting the number of layers of the falling film unit 12 disposed in the plug flow reactor. The more the number of layers of the falling film unit 12, the smaller the difference in residence time between materials, and the better the uniformity of the exchange reaction. In the present invention, it is preferred that the falling film assembly comprises 5 to 60 falling film units 12, more preferably 10 to 30 layers.

In a preferred embodiment of the present invention, the falling film unit 12 of the above-mentioned plug flow reactor comprises a perforated cover plate 8 and an overflow tray 9, wherein the overflow tray 9 is disposed in the porous cover plate along the flow direction of the material. Downstream of 8, there is an overflow port on the overflow tray 9. The perforated cover 8 is capable of dividing the material fluid and acting as a static mixture. In a more preferred embodiment of the present invention, the perforated cover plate 8 has a structure in which the center is convex upward, which facilitates the rapid flow of the material fluid to the periphery. The overflow port of the overflow tray 9 is located at the center of the overflow tray 9. This arrangement facilitates the flow of material under the action of its own gravity to the porous cover plate 8 of the lower falling film unit 12, thereby dispersing quickly. Go to the perimeter of the reaming cover.

In the above preferred embodiment, the perforated cover plate 8 is further preferably a conical umbrella plate having a tapered tapered conical plate for facilitating the overflow of the material fluid from the overflow tray 9 of the upper falling film unit 12. The flow port overflows to the center of the conical umbrella plate of the lower falling film unit 12, and then flows rapidly to the periphery of the cover plate by gravity. That is, the overflow port of the overflow tray 9 is facing the cone top of the conical umbrella plate, so that the material overflowing from the overflow tray 9 to the cone top of the conical umbrella plate will have a certain taper under the action of gravity. The umbrella plate flows faster around it.

In another exemplary embodiment of the present invention, a modified polyester production system is also provided, which can be seen from the flow chart for producing the modified polyester shown in FIG. In addition to the esterification system, precondensation system and final polycondensation system commonly used in the polyester production process, the system also includes an online additive addition system and the above-mentioned additives which are disposed between the esterification system and the precondensation system according to the material flow sequence. An exchange reaction system.

The above modified polyester production system provided by the invention can not only realize the oligomerization of the modifier in the polyester by adding the modifier online addition system and any of the above-mentioned exchange reaction systems in the common polyester production system. The addition of the modifier, and the exchange of the modifier with the polyester oligomer to achieve uniform distribution of the modifier in the polyester oligomer backbone, 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 modified polyester production system of the present invention, the modifier online addition system is a device for performing on-line real-time addition of a modifier to the polyester oligomer obtained by the esterification reaction from the esterification system. . In actual production, the modifier online additive device commonly used in the art can be appropriately adjusted according to the modifier to be added, and can be applied to the present invention. In a preferred embodiment of the present invention, as shown in FIG. 3, the modifier online addition system includes a modifier masterbatch in-line injection device and/or a modifier solution in-line injection device. The modifier masterbatch in-line injection device can realize the online addition of the solid particle modifier, and the modifier solution in-line injection device can realize the online addition of the liquid modifier solution, and simultaneously set the above two modifiers to be injected online. Simultaneous in-line addition of two or more liquid and solid modifiers can be achieved with the device.

In the above embodiment of the present invention, the modifier masterbatch in-line injection device can reasonably adjust the existing solid particle modifier on-line adding device, as long as the required solid particulate modifier can be added online. . Similarly, the in-line injection device for the modifier solution can be applied to the present invention only by appropriately adjusting the existing liquid modifier on-line adding device. In a more preferred embodiment of the present invention, the modifier masterbatch in-line injection device comprises a modifier masterbatch drying system, a screw extruder, a modifier masterbatch melt metering pump; The agent solution in-line injection device includes a modifier solution preparation tank, a modifier solution supply tank, a modifier solution metering pump, and a modifier solution injector which are sequentially connected.

The modifier masterbatch in-line injection device having the above structure can effectively connect the production process of the modifier masterbatch with the device to which the modifier is added, and can also change the required addition. Sex The amount of masterbatch is metered to achieve precise addition of the modifier. Similarly, the in-line injection device of the modifier solution in the above preferred embodiment of the present invention can simultaneously realize real-time modulation, supply, metering and precise addition of the desired modifier solution.

The above-mentioned modified polyester production system of the present invention is realized by mixing and dispersing a modifier in a polyester oligomer mainly by a static mixer of an agitator and an oligomer pipe of an esterification system in the prior art. Also included is a dynamic mixer as shown in Figure 3, which achieves a homogeneous mixing and dispersion of the modifier in the polyester oligomer in a dynamic mixing manner to achieve nearly homogeneous physical blending. In a preferred embodiment of the present invention, the dynamic mixer is a 1 to 5 high shear dynamic mixer, and the high shear dynamic mixer has better mixing effect on the material than the general dynamic mixer.

In the above modified polyester production system of the present invention, the amount of the polyester oligomer which can be produced can also be estimated by the amount of the raw material initially entering the esterification system, thereby estimating the amount of the modifier required. If the amount of the polyester oligomer is to be more accurately grasped in order to more accurately measure the amount of the modifier to be added, the above modified polyester production system of the present invention may further comprise an esterification in the order of material flow. An oligomer heat exchanger and an oligomer metering device between the system and the on-line addition system. The oligomer heat exchanger is capable of temperature-regulating the polyester oligomer from the esterification system to facilitate the addition and mixing of the modifier. The oligomer metering device accurately measures the amount of polyester oligomer that requires the addition of a modifier. More preferably, the oligomer delivery metering device comprises an oligomer pump and an oligomer flow meter disposed behind the oligomer pump.

In still another typical embodiment of the present invention, a method for preparing a modified polyester is further provided, which comprises the steps of separately preparing a slurry and a modifier; and adding the slurry to any of the above modifications. In the polyester production system, the modifier is added to an in-line addition system of any of the modified polyester production systems to obtain a modified polyester.

The preparation method of the above modified polyester of the present invention is prepared by using the above modified polyester production system, so that the modifier is uniformly distributed in the main chain of the polyester molecule, thereby making the height of the modified polyester structure prepared. Uniform, suitable for the production of high quality fiber and film products.

In the above preparation method of the present invention, the slurry is prepared by using a dibasic acid and a glycol as a raw material according to a conventional method in the art. Among them, the dibasic acid is most commonly used in terephthalic acid, and the glycol is at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, and cyclohexane dimethanol. The formulation process of the modifier varies depending on the type of modifier. In a preferred embodiment of the invention, a modifier having a kinetic viscosity of from 0.05 Pa.s to 1000 Pa.s is formulated during the preparation of the modifier. The preferred dynamic viscosity of the modifier solution is 0.05 to 5 Pa.s, and the preferred dynamic viscosity of the modifier masterbatch melt is 5 to 1000 Pa.s. The modifier in the dynamic viscosity range can be uniformly mixed with the polyester oligomer via a dynamic mixer.

In the above preparation method of the present invention, the reaction temperature of the esterification system is the temperature commonly used in the esterification reaction in the art, that is, 200 to 280 ° C, and the degree of polymerization of the polyester oligomer after the esterification reaction is 1 to 8. The polyester oligomer having a lower degree of polymerization is relatively easy to achieve blending or copolymerization with the modifier.

In the above preparation method of the present invention, when the modified polyester production system includes the oligomer heat exchanger, the oligomer heat exchanger adjusts the oligomer temperature to 180 to 300 °C. Adjusting the temperature of the oligomer to the above temperature range enables the temperature of the polyester oligomer to be close to the temperature of the modifier to be added, thereby reducing the adverse reaction caused by the temperature difference.

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

In the above preparation method of the present invention, the exchange reaction system differs slightly depending on the material in which the exchange reaction actually takes place, and the reaction temperature and reaction time are also slightly different. In a preferred embodiment of the invention, the temperature of the exchange reaction is from 180 to 300 ° C, and the reaction time is from 10 to 180 min. The temperature and reaction time of the exchange reaction are controlled within the above range, and the high-efficiency dispersion of the modifier in the polyester oligomer and the near-homogeneous reaction of the exchange reaction can be achieved, and the modifier is dispersed as uniformly as possible in the polyester. On the main chain of the polymer. In addition, the degree of exchange reaction can be effectively controlled by adjusting the reaction temperature and residence time of the materials in the plug flow reactor of the exchange system to obtain a structurally modified polyester oligomer.

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

In another exemplary embodiment of the present invention, there is also provided a modified polyester fiber product prepared from the modified polyester produced by any of the above modified polyester production systems. The modified polyester fiber product provided by the invention has a breaking strength of 2.5-6.0 cN/dtex, an elongation at break of 20-50%, and a dyeing uniformity of 4-5, not only the breaking strength and elongation at break of the fiber. The requirements for subsequent weaving can be satisfied, and the dyeing uniformity is higher than that of the modified polyester fiber product prepared in the prior art, indicating that the modified polyester fiber product provided by the present invention has higher structural uniformity.

Advantageous effects of the present invention will be further described below in conjunction with specific embodiments.

It should be noted that, according to the embodiment of the present invention, the preparation of the modified polyester is carried out according to the flow shown in FIG. 2, and further, according to the flow shown in FIG. 3, the addition of the modifier and the dynamic mixing of the physical blending are performed. The exchange reaction system shown in Fig. 1 performs an exchange reaction. In Fig. 1, reference numeral 1 is the material inlet to be exchanged, 2 is a vertical full mixed flow reactor, 3 is a heated inner coil assembly, 4 is a stirrer motor, 5 is a stirring rod, and 6 is an axisymmetric setting. Stirring paddle, 7 is a flat push reactor, 8 is a conical umbrella plate, 9 is an overflow tray, 10 is a material outlet after exchange reaction, 11 is a stirrer, and 12 is a falling film unit.

Example 1

The slurry prepared by blending terephthalic acid and ethylene glycol was continuously and uniformly conveyed at a flow rate of 2964 kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction at a reaction temperature of 265 °C. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the esterification vessel at a flow rate of 35.9 kg/h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2470 kg/h. It is produced in an esterification kettle.

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

The oligomer and the modifier polycaprolactam masterbatch melt are uniformly mixed by a 5-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 250 ° C, the rotation speed is 3000 r / min, exchange The vertical full-flow reactor of the reaction system has a length-to-diameter ratio of 1.5 and a number of mixing paddles of three groups. The vertical-type push-flow reactor has an aspect ratio of 10 and a falling film unit of 20 layers. The diameter of the mixed flow reactor is twice that of the vertical flat flow reactor. The oligomer and modifier polycaprolactam masterbatch melt blend is obtained by an ester-amide exchange reaction in the exchange reaction system to obtain a polyethylene terephthalate/caprolactam copolymer, which is directly transported by an oligomer pump to The precondensation reaction system performs a precondensation reaction in which the reaction temperature of the exchange reaction system is 260 ° C and the reaction time is 90 min.

The precondensation reaction system consisted of a vertical polycondensation kettle having a reaction temperature of 270 °C. When the intrinsic viscosity of the prepolymer reached 0.30 dL/g, it was continuously and stably collected from the pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle with a reaction temperature of 280 ° C. When the intrinsic viscosity of the final polymer reaches 0.80 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber was a hydrophilic polyester fiber having a breaking strength of 4.1 cN/dtex, an elongation at break of 38%, and a dyeing uniformity of 5 grades. The dyeing results of the fiber indicate that the molecular band of the modifier polycaprolactam is uniformly distributed in the main chain of the polyester molecule, so that the hydrophilic polyester structure is uniform, and the fiber dyeing has no color difference.

Example 2

The slurry prepared by blending terephthalic acid and ethylene glycol was continuously and uniformly conveyed at a flow rate of 2964 kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction at a reaction temperature of 261 °C. A catalyst of cerium acetate having a concentration of 3.5% by weight was continuously and uniformly injected into the esterification vessel at a flow rate of 41.5 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 4, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2246 kg/h. It is produced in an esterification kettle.

The oligomer from the esterification reaction system is cooled to 230 ° C by a Sulzer-type heat exchanger and the modifier diethylene glycol isophthalate-5-sulfonate is injected from the in-line injection device of the modifier solution. The solution enters the dynamic mixer together. The concentration of diethylene glycol isophthalate-5-sulfonic acid sodium solution is 25wt%, the injection temperature is 90 ° C, the injection flow rate is 186 kg / h, the dynamic viscosity is 0.1 Pa.s, and the isophthalic acid diethyl ether The process of injecting the sodium glycol-5-sulfonate solution is: adding the sodium diethylene isophthalate-5-sulfonate esterification solution to the modifier solution preparation tank and preparing the ethylene glycol to form The solution with a concentration of 25wt% is transferred to the modifier solution supply tank by the difference, and the metering flow rate of the oligomer is measured by the modifier solution metering pump according to the flow ratio of the output oligomer of the oligomer delivery metering device. Inject the dynamic mixer feed line.

The oligomer and the modifier sodium diethylene glycol isophthalate-5-sulfonate solution are uniformly mixed by a 3-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 230 ° C, the rotation speed is 1000r / min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 1, the number of the stirring paddles is two, the length-to-diameter ratio of the vertical flat-flow reactor is 4, the falling film The number of unit layers is 8 layers, and the diameter of the vertical full mixed flow reactor is 1.2 times the diameter of the vertical flat flow reactor. Blend of oligomer and modifier diethylene glycol isophthalate-5-sulfonate solution in a exchange reaction system to obtain ethylene terephthalate/isophthalic acid by transesterification After the ethylene glycol ester-5-sulfonic acid sodium oligomer is directly transported by an oligomer pump to a precondensation reaction system for pre-polycondensation reaction, the reaction temperature of the exchange reaction system is 235 ° C, and the reaction time is 40 min.

The precondensation reaction system consisted of a vertical precondensation kettle in which the temperature of the reactants in the precondensation kettle was 260 °C. When the intrinsic viscosity of the prepolymer reached 0.15 dL/g, it was continuously and stably collected from the pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle in which the final polycondensation kettle had a reaction temperature of 275 °C. When the intrinsic viscosity of the final polymer reaches 0.50 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a cationic dye-dyeable polyester fiber: the fiber has a breaking strength of 3.0 cN/dtex, an elongation at break of 32%, and a dyeing uniformity of 4.5. The dyeing results of the fiber indicate that the modifier diethylene isophthalate-5-sulfonate sodium segment is uniformly distributed in the polyester molecular main chain, so that the cationic dye dyeable polyester structure is uniform, and the fiber dyeing is not Color difference.

Example 3

The slurry prepared by blending terephthalic acid and ethylene glycol was continuously and uniformly conveyed at a flow rate of 2,808 kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction at a reaction temperature of 260 °C. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the esterification vessel at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 3, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2340 kg/h. It is produced in an esterification kettle.

The oligomer from the esterification reaction system is cooled by a multi-tube heat exchanger to 240 ° C and then enters with the modifier polybutylene terephthalate masterbatch melt from the modifier masterbatch in-line injection unit. Dynamic mixer, polybutylene terephthalate masterbatch melt injection temperature of 240 ° C, injection flow rate of 250 kg / h, dynamic viscosity of 450 Pa.s, of which polybutylene terephthalate masterbatch The injection process is: the polybutylene 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 transport metering. The flow ratio of the output oligomer of the device controls the metered flow and is directly injected into the feed line of the dynamic mixer.

The oligomer and the modifier polybutylene terephthalate masterbatch melt are uniformly mixed by a 5-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 240 ° C, The rotation speed is 1500r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 2, the number of the stirring paddles is 4, the length-to-diameter ratio of the vertical flat-flow reactor is 15, and the number of falling film units For the 30-layer, the vertical full-flow reactor has a diameter 1.5 times that of the vertical flat-flow reactor. The oligomer and the modifier polybutylene terephthalate masterbatch melt blend obtains ethylene terephthalate/butylene terephthalate by transesterification in an exchange reaction system. After the copolymer, it was directly transferred from the oligomer pump to the precondensation reaction system for pre-polycondensation reaction, wherein the reaction temperature of the exchange reaction system was 250 ° C and the reaction time was 150 min.

The pre-polycondensation reaction system consists of a vertical first pre-condensation kettle and a horizontal second pre-condensation kettle, wherein the first pre-condensation kettle has a reactant temperature of 260 ° C and the second pre-condensation kettle has a reactant temperature of 265 ° C. When the intrinsic viscosity of the prepolymer reached 0.40 dL/g, it was continuously and stably collected from the second pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle with a reaction temperature of 270 ° C. When the intrinsic viscosity of the final polymer reaches 0.90 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a disperse dye atmospheric pressure dyeable polyester fiber: breaking strength is 4.2 cN/dtex, elongation at break is 45%, and dyeing uniformity is 4.5. The dyeing results of the fiber indicate that the molecular block of the modifier polybutylene terephthalate is uniformly distributed in the main chain of the polyester molecule, so that the disperse dye has a uniform structure of the atmospheric pressure dyeable polyester, and the fiber dyeing has no color difference.

Example 4

The slurry prepared by blending terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2496 kg/h to an esterification reaction system composed of a vertical first esterification kettle and a horizontal second esterification kettle for esterification. The reaction temperature was 265 ° C in the first esterification kettle and 268 ° C in the second esterification reactor. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 8, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2080 kg/h. The second esterification kettle is produced.

The oligomer from the esterification reaction system is heated to 300 ° C in a multi-tube heat exchanger and then combined with the modifier polybutylene terephthalate masterbatch melt from the modifier masterbatch in-line injection unit. Into the dynamic mixer, the polytetramethylene terephthalate masterbatch melt injection temperature is 300 ° C, the injection flow rate is 500 kg / h, the dynamic viscosity is 300 Pa.s, of which polyethylene terephthalate The process of ester masterbatch injection is as follows: the polybutylene 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 low The flow ratio of the output of the polymer delivery metering device to the oligomer controls the metering flow and is directly injected into the feed line of the dynamic mixer.

The oligomer and the modifier poly(cyclohexanemethanol) masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 300 ° C. The speed is 2000r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 3, the number of stirring paddles is 5, and the length-to-diameter ratio of the vertical flat-flow reactor is 12, the falling film unit The number is 24 layers, and the diameter of the vertical full mixed reaction reactor is 1.8 times the diameter of the vertical flat flow reactor. Oligomer and modifier polybutylene terephthalate masterbatch melt blend obtained by transesterification in an exchange reaction system to obtain ethylene terephthalate / cyclohexane After the methanol ester copolymer, it is directly sent from the oligomer pump to the precondensation reaction system for pre-polycondensation reaction, wherein the reaction temperature of the exchange reaction system is 300 ° C, and the reaction time is 100 min.

The precondensation reaction system consisted of a vertical first pre-condensation kettle and a horizontal second pre-condensation kettle, wherein the first pre-condensation kettle had a reactant temperature of 295 ° C and the second pre-condensation kettle had a reactant temperature of 290 ° C. When the intrinsic viscosity of the prepolymer reached 0.20 dL/g, it was continuously and stably collected from the second pre-polycondensation vessel by a prepolymer pump and sent to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation kettle, and the reaction temperature of the final polycondensation kettle is 290 ° C. When the intrinsic viscosity of the final polymer reaches 0.70 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a disperse dye atmospheric pressure dyeable polyester fiber: a breaking strength of 4.8 cN/dtex, an elongation at break of 25%, and a dyeing uniformity of 4 grades. The dyeing results of the fiber indicate that the molecular segment of the modifier poly(cyclohexanedimethylene terephthalate) is uniformly distributed in the main chain of the polyester molecule, so that the disperse dye has a uniform structure of the atmospheric pressure dyeable polyester, and the fiber dyeing has no color difference.

Example 5

The slurry prepared by blending terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2784 kg/h to an esterification reaction system composed of a vertical first esterification kettle and a horizontal second esterification kettle for esterification. The reaction temperature was 265 ° C in the first esterification kettle and 268 ° C in the second esterification reactor. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 35.9 kg/h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 6, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 1820 kg/h. The second esterification kettle is produced.

The oligomer from the esterification reaction system is heated to 290 ° C by a Sulzer-type heat exchanger and then enters with the modifier polyethylene naphthalate masterbatch melt from the modifier masterbatch in-line injection device. The dynamic mixer, the polyethylene naphthalate masterbatch melt has an injection temperature of 290 ° C, an injection flow rate of 750 kg / h, and a dynamic viscosity of 600 Pa.s, wherein the polyethylene naphthalate masterbatch is injected. The process flow is: the polyethylene naphthalate 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 output of the oligomer transport metering device. The flow ratio of the polymer controls the metered flow and is injected directly into the feed line of the dynamic mixer.

The oligomer and the modifier polyethylene naphthalate masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 290 ° C, the rotation speed For 5000r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 2, the number of stirring paddles is 4, the length-to-diameter ratio of the vertical flat-flow reactor is 20, and the number of falling film units is The 40-layer, vertical full-flow reactor is three times the diameter of the vertical flat-flow reactor. The oligomer and the modifier polyethylene naphthalate masterbatch melt blend are subjected to a transesterification reaction in an exchange reaction system to obtain a polyethylene terephthalate/naphthalene diethylene glycol copolymer. Thereafter, the oligomerization pump directly transported to the pre-polycondensation reaction system for pre-polycondensation reaction, wherein the reaction temperature of the exchange reaction system was 290 ° C and the reaction time was 180 min. .

The precondensation reaction system consisted of a vertical first pre-polycondensation kettle and a horizontal second pre-polycondensation kettle, wherein the first pre-condensation kettle had a reactant temperature of 280 ° C and the second pre-condensation kettle had a reactant temperature of 285 ° C. When the intrinsic viscosity of the prepolymer reaches 0.20 dL/g, it is continuously and stably collected from the second pre-polycondensation kettle by a prepolymer pump and sent to the final polycondensation system. Final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle with a reaction temperature of 290 ° C. When the intrinsic viscosity of the final polymer reaches 0.65 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber was a high modulus polyester fiber having a breaking strength of 6.0 cN/dtex, an elongation at break of 24%, and a dyeing uniformity of 4 grades. The dyeing results of the fiber indicate that the molecular band of the modifier polyethylene naphthalate is uniformly 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 prepared by blending terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2784 kg/h to an esterification reaction system composed of a vertical first esterification kettle and a horizontal second esterification kettle for esterification. The reaction temperature was 260 ° C in the first esterification kettle and 265 ° C in the second esterification reactor. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 5, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 1820 kg/h. The second esterification kettle is produced.

The oligomer from the esterification reaction system is cooled by a Sulzer-type heat exchanger to 230 ° C and enters the dynamics together with the modifier polytrimethylene terephthalate masterbatch melt from the modifier masterbatch in-line injection unit. The mixer, the polytrimethylene terephthalate masterbatch melt has an injection temperature of 230 ° C, an injection flow rate of 750 kg / h, a dynamic viscosity of 150 Pa.s, wherein the polytrimethylene terephthalate master batch injection process is : The polytrimethylene terephthalate masterbatch is dried by a modifier masterbatch drying system, melted by a screw extruder, and passed through a modifier masterbatch melt metering pump to output an oligomer flow rate according to the oligomer transport metering device. The proportional control metering flow is injected directly into the feed line of the dynamic mixer.

The oligomer and the modifier polytrimethylene terephthalate masterbatch melt are uniformly mixed by a 4-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the dynamic mixer has a temperature of 230 ° C and a rotation speed of 4000r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 3, the number of stirring paddles is 5, the length-to-diameter ratio of the vertical flat-flow reactor is 18, and the number of falling film units is 36. The diameter of the vertical full-flow reactor is four times that of the vertical flat-flow reactor. After the oligomer and modifier polytrimethylene terephthalate masterbatch melt blend is obtained by transesterification to obtain a polyethylene terephthalate/trimethylene terephthalate copolymer in an exchange reaction system, The prepolymerization reaction is carried out directly from the oligomer pump to the precondensation reaction system, wherein the reaction temperature of the exchange reaction system is 230 ° C and the reaction time is 160 min.

The precondensation reaction system consisted of a vertical precondensation kettle with a reaction temperature of 245 °C. When the intrinsic viscosity of the prepolymer reached 0.40 dL/g, it was continuously and stably collected from the precondensation kettle by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation reactor, and the reaction of the final polycondensation reactor The temperature is 255 °C. When the intrinsic viscosity of the final polymer reaches 0.95 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a disperse dye atmospheric pressure dyeable polyester fiber: breaking strength is 3.2 cN/dtex, elongation at break is 50%, disperse dye has a normal dye uptake rate of 95%, and dyeing uniformity is 4.5. The dyeing results of the fiber indicate that the molecular block of the modifier polytrimethylene terephthalate is uniformly distributed in the main chain of the polyester molecule, so that the disperse dye has a uniform structure of the atmospheric pressure dyeable polyester, and the fiber dyeing has no color difference.

Example 7

The slurry prepared by blending terephthalic acid and ethylene glycol was continuously and uniformly conveyed at a flow rate of 2964 kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction at a reaction temperature of 265 °C. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the esterification vessel at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 7, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2470 kg/h. It is produced in an esterification kettle.

The oligomer from the esterification reaction system is heated to 270 ° C in a single tube heat exchanger and then enters the dynamic mixture together with the modifier polyhexamethylene adipamide masterbatch melt from the modifier masterbatch in-line injection device. The injection temperature of the polyhexamethylene adipamide masterbatch melt is 270 ° C, the injection flow rate is 125 kg / h, and the dynamic viscosity is 250 Pa.s, wherein the process of injecting the polyhexamethylene adipamide masterbatch is: The polyhexamethylene adipamide masterbatch is dried by a modifier masterbatch drying system, melted by a screw extruder, and the ratio of the flow rate of the oligomer discharged by the modifier masterbatch melt metering device according to the oligomer transport metering device The metered flow is controlled and injected directly into the feed line of the dynamic mixer.

The oligomer and the modifier polyhexamethylene adipamide masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the dynamic mixer has a temperature of 270 ° C and a rotation speed of 2500r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 1.8, the number of stirring paddles is 3, the length-to-diameter ratio of the vertical flat-flow reactor is 15, and the number of falling film units is 30. The diameter of the vertical full-flow reactor is 5 times the diameter of the vertical flat-flow reactor. Oligomer and Modifier Polyhexamethylene Adipamide Masterbatch Melt Blend Obtained ethylene terephthalate / hexamethylene adipamide copolymer by ester-amide exchange reaction in an exchange reaction system Thereafter, the oligomerization pump directly transports to the pre-polycondensation reaction system for pre-polycondensation reaction, wherein the exchange reaction system has a reaction temperature of 265 ° C and a reaction time of 120 min.

The precondensation reaction system consisted of a vertical first pre-condensation kettle and a horizontal second pre-condensation kettle, wherein the first pre-condensation kettle had a reactant temperature of 265 ° C and the second pre-condensation kettle had a reactant temperature of 267 ° C. When the intrinsic viscosity of the prepolymer reached 0.15 dL/g, it was continuously and stably collected from the second pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation kettle, and the reaction temperature of the final polycondensation kettle is 270 ° C. When the intrinsic viscosity of the final polymer reaches 0.78 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber was a hydrophilic polyester fiber having a breaking strength of 4.2 cN/dtex, an elongation at break of 32%, and a dyeing uniformity of 5 grades. The dyeing results of the fiber indicate that the molecular segment of the modifier polyhexamethylene adipamide is uniformly distributed in the main chain of the polyester molecule, so that the hydrophilic polyester structure is uniform, and the fiber dyeing has no color difference.

Example 8

The slurry prepared by blending terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2808 kg/h to an esterification reaction system composed of a vertical first esterification kettle and a horizontal second esterification kettle for esterification. The reaction temperature was 262 ° C in the first esterification kettle and 267 ° C in the second esterification reactor. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 35.9 kg/h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 6, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2080 kg/h. The second esterification kettle is produced.

The oligomer from the esterification reaction system is heated to 300 ° C in a Sulzer-type heat exchanger and enters the dynamics together with the modifier polyadipyl butadiene diamine masterbatch melt from the modifier masterbatch in-line injection unit. The mixer, the polyadipyl diamine diamine masterbatch melt has an injection temperature of 300 ° C, an injection flow rate of 250 kg / h, and a kinematic viscosity of 1000 Pa.s, wherein the process of injecting the polyadipyl succinimide masterbatch is : The polyadipyl succinimide masterbatch is dried by a modifier masterbatch drying system, melted by a screw extruder, and passed through a modifier masterbatch melt metering pump to output an oligomer flow rate according to the oligomer transport metering device. The proportional control metering flow is injected directly into the feed line of the dynamic mixer.

The oligomer and the modifier polyadipyl amide diamine masterbatch melt are uniformly mixed by a 4-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the dynamic mixer has a temperature of 300 ° C and a rotation speed of 2000r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 3, the number of mixing paddles is 4, the length-to-diameter ratio of the vertical flat-flow reactor is 10, and the number of falling film units is 20 The diameter of the vertical full-flow reactor is 2.5 times the diameter of the vertical flat-flow reactor. Oligomer and modifier polyadipyl diamine masterbatch melt blend obtained in the exchange reaction system by ester-amide exchange reaction to obtain ethylene terephthalate / adipyl butyl diamine copolymer Thereafter, the oligomerization pump directly transports to the pre-polycondensation reaction system for pre-polycondensation reaction, wherein the exchange reaction system has a reaction temperature of 295 ° C and a reaction time of 90 min.

The pre-polycondensation reaction system consists of a vertical first pre-condensation kettle and a horizontal second pre-condensation kettle, wherein the first pre-condensation kettle has a reactant temperature of 295 ° C and the second pre-condensation kettle has a reactant temperature of 300 ° C. When the intrinsic viscosity of the prepolymer reached 0.20 dL/g, it was continuously and stably collected from the second pre-polycondensation vessel by a prepolymer pump and sent to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation kettle, and the reaction temperature of the final polycondensation kettle is 300 ° C. When the intrinsic viscosity of the final polymer reaches 0.85 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber was a hydrophilic polyester fiber having a breaking strength of 3.8 cN/dtex, an elongation at break of 42%, and a dyeing uniformity of 4.5. The dyeing results of the fiber indicate that the molecular segment of the modifier polyadipyldiamine diamine is uniformly distributed in the main chain of the polyester molecule, so that the hydrophilic polyester structure is uniform, and the fiber dyeing has no color difference.

Example 9

The slurry prepared by blending terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2808 kg/h to an esterification reaction system composed of a vertical first esterification kettle and a horizontal second esterification kettle for esterification. The reaction temperature was 264 ° C in the first esterification kettle and 267 ° C in the second esterification reactor. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 5, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2340 kg/h. The second esterification kettle is produced.

The oligomer from the esterification reaction system is cooled to 250 ° C by a multi-tube heat exchanger and enters the dynamic mixer together with the modifier polyethylene glycol solution from the in-line injection device of the modifier solution, 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 process of injecting polyethylene glycol solution is: adding polyethylene glycol to the modifier solution to prepare The tank is prepared with a solution of ethylene glycol to a concentration of 90% by weight, and then transferred to the modifier solution supply tank through the difference, and the metering pump of the modifier solution is used to control the flow rate of the oligomer according to the output of the oligomer delivery metering device. The flow is then injected into the dynamic mixer feed line by a modifier solution injector.

The oligomer and the modifier polyethylene glycol solution are uniformly mixed by a 2-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 230 ° C, the rotation speed is 3500 r / min, and the exchange reaction The length-to-diameter ratio of the vertical full-flow reactor of the system is 2, the number of mixing paddles is 4, the length-to-diameter ratio of the vertical flat-flow reactor is 5, the number of falling film units is 10, and the vertical full-flow The diameter of the reactor was 1.5 times the diameter of the vertical plug flow reactor. The oligomer and modifier polyethylene glycol solution blend is obtained by transesterification reaction to obtain ethylene terephthalate/polyethylene glycol copolymer in an exchange reaction system, and then directly transported by an oligomer pump to The precondensation reaction system performs a precondensation reaction in which the reaction temperature of the exchange reaction system is 250 ° C and the reaction time is 45 min.

The precondensation reaction system consisted of a vertical precondensation kettle in which the temperature of the reactants in the precondensation kettle was 275 °C. When the intrinsic viscosity of the prepolymer reached 0.30 dL/g, it was continuously and stably collected from the pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle in which the reaction temperature of the final polycondensation kettle was 280 °C. When the intrinsic viscosity of the final polymer reaches 0.90 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

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

Example 10

The slurry prepared by blending terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2902 kg/h to an esterification reaction system composed of a vertical first esterification kettle and a horizontal second esterification kettle for esterification. The reaction temperature was 260 ° C in the first esterification kettle and 265 ° C in the second esterification reactor. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 5, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2418 kg/h. The second esterification kettle is produced.

The oligomer from the esterification reaction system is cooled to 255 ° C by a single-tube mixing heat exchanger and the flame retardant 2-carboxyethylphenylphosphinic acid ethylene glycol ester solution from the in-line injection device of the modifier solution Entering the dynamic mixer together, the concentration of the 2-carboxyethylphenylphosphinic acid ethylene glycol solution is 50% by weight, the injection temperature is 60 ° C, the injection flow rate is 490 kg / h, and the dynamic viscosity is 1.5 Pa.s, of which 2 - The injection process of carboxyethylphenylphosphinic acid ethylene glycol solution is: adding esterification solution of ethylene glycol 2-carboxyethylphenylphosphinic acid ester with esterification rate of 85% to the modifier The solution is adjusted to a concentration of 50% by weight with ethylene glycol, and then transferred to the modifier solution supply tank by the difference, and the ratio of the flow rate of the oligomer output by the modifier solution metering pump according to the oligomer delivery metering device is The metering flow is controlled and injected into the dynamic mixer feed line by the modifier solution injector.

The oligomer and the modifier 2-carboxyethylphenylphosphinic acid ethylene glycol solution are uniformly mixed by a 5-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 230. °C, rotation speed 50r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 0.5, the number of mixing paddles is 2, and the length-to-diameter ratio of the vertical flat-flow reactor is 2. The number is 4 layers, and the diameter of the vertical full mixed reactor is 1.05 times the diameter of the vertical flat flow reactor. Blend of oligomer and modifier 2-carboxyethylphenylphosphinic acid ethylene glycol solution to obtain ethylene terephthalate/2-carboxyethylbenzene by transesterification in an exchange reaction system After the ethylene phosphinate copolymer is directly transferred from the oligomer pump to the precondensation reaction system for pre-polycondensation reaction, the reaction temperature of the exchange reaction system is 255 ° C, and the reaction time is 10 min.

The precondensation reaction system consisted of a vertical first pre-condensation kettle and a horizontal second pre-polycondensation kettle, wherein the first pre-condensation kettle had a reactant temperature of 265 ° C and the second pre-condensation kettle had a reactant temperature of 270 ° C. When the intrinsic viscosity of the prepolymer reached 0.10 dL/g, it was continuously and stably collected from the second pre-polycondensation vessel by a prepolymer pump and sent to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation kettle and a horizontal liquid phase thickening kettle, wherein the reaction temperature of the final polycondensation kettle is 275 ° C, and the reaction temperature of the liquid phase thickening kettle is 280 ° C. When tackifying the properties of the final polymer The viscosity reaches 0.75 dL/g, and the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun to obtain a modified polyester fiber.

The fiber is a flame-retardant polyester fiber having a breaking strength of 2.8 cN/dtex, an elongation at break of 25%, and a dyeing uniformity of 4.5. The fiber dyeing results show that the flame retardant 2-carboxyethylphenylphosphinic acid ethylene glycol segment is evenly distributed in the polyester molecular main chain, so that the flame retardant polyester structure is uniform, and the fiber dyeing has no color difference.

Example 11

The slurry prepared by mixing terephthalic acid and butanediol is continuously and uniformly conveyed at a flow rate of 2496 kg/h to esterification composed of a second esterification tank composed of a vertical first esterification tank and a horizontal belt compartment structure. The esterification reaction was carried out in the reaction system, the first esterification tank reaction temperature was 230 ° C, and the second esterification reactor reaction temperature was 240 ° C. The esterification catalyst tetrabutyl titanate solution having a concentration of 3 wt% was continuously and uniformly injected into the first esterification kettle at a flow rate of 41.7 kg/h; the condensation polymerization catalyst tetrabutyl titanate and ruthenium acetate composite catalyst at a concentration of 5 wt%; The solution was continuously and uniformly injected into the third compartment of the second esterification kettle at a flow rate of 41.7 kg/h. When the degree of polymerization of the esterified butylene terephthalate oligomer reaches 1, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2080 kg/h. It is produced in an esterification kettle.

The oligomerized Sulzer-type heat exchanger from the esterification reaction system is cooled to 180 ° C and enters the dynamics together with the modifier polybutylene succinate masterbatch melt from the modifier masterbatch in-line injection unit. Mixer, polybutylene succinate masterbatch melt injection temperature is 160 ° C, injection flow rate is 500 kg / h, dynamic viscosity is 800 Pa.s, wherein polybutylene succinate mother particle injection process The process is as follows: the polybutylene succinate masterbatch is dried by a modifier masterbatch drying system, melted by a screw extruder, and output oligomerized by a modifier masterbatch melt metering pump according to the oligomer transport metering device. The flow ratio of the material controls the metered flow and is directly injected into the feed line of the dynamic mixer.

The oligomer and the 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, wherein the dynamic mixer temperature is 180 ° C, the rotation speed For 3000r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 2, the number of stirring paddles is 4, the length-to-diameter ratio of the vertical flat-flow reactor is 10, and the number of falling film units is The 30-layer, vertical full-flow reactor has twice the diameter of the vertical flat-flow reactor. Olefin and Modifier Polybutylene succinate Masterbatch Melt Blend Derivatives of Butylene Terephthalate / Butylene Succinate Copolymer by Transesterification in an Exchange Reaction System Thereafter, it was directly sent from an oligomer pump to a precondensation reaction system for pre-polycondensation reaction, wherein the temperature of the exchange reaction system was 180 ° C, and the reaction time was 90 min.

The precondensation reaction system consisted of a vertical precondensation kettle in which the temperature of the reactants in the precondensation kettle was 200 °C. When the intrinsic viscosity of the prepolymer reached 0.50 dL/g, it was continuously and stably collected from the pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation kettle, in which the final polycondensation The reaction temperature of the kettle was 200 °C. When the intrinsic viscosity of the final polymer reaches 1.20 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a biodegradable polyester fiber having a breaking strength of 3.0 cN/dtex, an elongation at break of 45%, and a dyeing uniformity of four. The fiber dyeing results show that the molecular segment of the modifier polybutylene succinate is uniformly distributed in the main chain of the polyester molecule, so that the biodegradable polyester has a uniform structure and the fiber dyeing has no color difference.

Example 12

The slurry prepared by mixing terephthalic acid and butanediol was continuously and uniformly conveyed at a flow rate of 2328 kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction at a reaction temperature of 230 °C. A catalyst having a concentration of 10% by weight of the catalyst tetraisopropyl titanate was continuously and uniformly injected into the esterification vessel at a flow rate of 17.5 kg/h. When the polymerization degree of the esterified butylene terephthalate oligomer reaches 2, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 1820 kg/h. It is produced in an esterification kettle.

The oligomeric Sulzer-type heat exchanger from the esterification reaction system is cooled to 200 ° C and enters the dynamics together with the modifier polybutylene adipate masterbatch melt from the modifier masterbatch in-line injection unit. The mixer, the polybutylene adipate masterbatch melt injection temperature is 200 ° C, the injection flow rate is 750 kg / h, the dynamic viscosity is 5 Pa.s, wherein the polybutylene adipate mother particle injection process The process is as follows: the polybutylene adipate masterbatch is dried by a modifier masterbatch drying system, melted by a screw extruder, and output oligomerized by a modifier masterbatch melt metering pump according to the oligomer transport metering device. The flow ratio of the material controls the metered flow and is directly injected into the feed line of the dynamic mixer.

The oligomer and the modifier polybutylene adipate masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the dynamic mixer has a temperature of 200 ° C and a rotation speed. For 4000r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 3, the number of stirring paddles is 5, the length-to-diameter ratio of the vertical flat-flow reactor is 15, and the number of falling film units is The 40-layer, vertical full mixed-flow reactor has a diameter five times that of the vertical flat-flow reactor. Oligomer and Modifier Polybutylene Adipate Masterbatch Melt Blend Derivatives of Butylene Terephthalate / Butylene Adipate Copolymer by Transesterification in an Exchange Reaction System Thereafter, it was directly sent from the oligomer pump to the precondensation reaction system for pre-polycondensation reaction, wherein the temperature of the exchange reaction system was 200 ° C, and the reaction time was 120 min.

The precondensation reaction system consisted of a vertical precondensation kettle in which the reactant temperature of the precondensation kettle was 210 °C. When the intrinsic viscosity of the prepolymer reached 0.45 dL/g, it was continuously and stably collected from the pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation kettle in which the reaction temperature of the final polycondensation kettle is 220 °C. When the intrinsic viscosity of the final polymer reaches 1.50 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a biodegradable polyester fiber having a breaking strength of 2.7 cN/dtex, an elongation at break of 50%, and a dyeing uniformity of 4.5. The fiber dyeing results show that the molecular segment of the modifier polybutylene adipate is uniformly distributed in the main chain of the polyester molecule, so that the biodegradable polyester has a uniform structure and the fiber dyeing has no color difference.

Example 13

The slurry prepared by mixing terephthalic acid and butanediol was continuously and uniformly conveyed at a flow rate of 2993 kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction at a reaction temperature of 230 °C. A catalyst having a concentration of 10% by weight of the catalyst tetraisopropyl titanate was continuously and uniformly injected into the esterification vessel at a flow rate of 17.5 kg/h. When the polymerization degree of the esterified butylene terephthalate oligomer reaches 3, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 1820 kg/h. It is produced in an esterification kettle.

The oligomer Sulzer-type heat exchanger from the esterification reaction system is cooled to 200 ° C and enters the dynamics together with the modifier polyethylene adipate masterbatch melt from the modifier masterbatch in-line injection unit. Mixer, polyethylene adipate glycol masterbatch melt injection temperature of 180 ° C, injection flow rate of 250 kg / h, dynamic viscosity of 60 Pa.s, wherein the process of polyethylene adipate glycol pellet injection The process is as follows: the polyethylene adipate glycol masterbatch is dried by the modifier masterbatch drying system, melted by a screw extruder, and output oligomerized by the modifier masterbatch melt metering pump according to the oligomer transport metering device. The flow ratio of the material controls the metered flow and is directly injected into the feed line of the dynamic mixer.

The oligomer and the modifier polyethylene adipate masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the dynamic mixer has a temperature of 200 ° C and a rotation speed. For 2000r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 2, the number of stirring paddles is 4, the length-to-diameter ratio of the vertical planter reactor is 10, and the number of falling film units is The 25-layer, vertical full-flow reactor has a diameter that is 3.5 times the diameter of the vertical flat-flow reactor. Olefin and Modifier Polyethylene Adipate Masterbatch Melt Blend Depolymerization of Butylene Terephthalate/Ethylene Adipate by Transesterification in an Exchange Reaction System After the product, the oligomerization pump directly transported to the pre-polycondensation reaction system for pre-polycondensation reaction, wherein the temperature of the exchange reaction system was 220 ° C, and the reaction time was 75 min.

The precondensation reaction system consisted of a vertical precondensation kettle in which the reactant temperature of the precondensation kettle was 230 °C. When the intrinsic viscosity of the prepolymer reached 0.30 dL/g, it was continuously and stably collected from the pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle in which the reaction temperature of the final polycondensation kettle was 240 °C. When the intrinsic viscosity of the final polymer reaches 1.30 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a biodegradable polyester fiber having a breaking strength of 3.4 cN/dtex, an elongation at break of 28%, and a dyeing uniformity of 5 grades. The fiber dyeing results show that the molecular segment of the modifier polyethylene adipate is uniformly distributed in the main chain of the polyester molecule, so that the biodegradable polyester has a uniform structure and the fiber dyeing has no color difference.

Example 14

The slurry prepared by mixing terephthalic acid and propylene glycol is continuously and uniformly conveyed at a flow rate of 3026 kg/h to an esterification reaction system consisting of a vertical first esterification kettle and a horizontal zone compartment structure second esterification kettle. The esterification reaction has a first esterification tank reaction temperature of 225 ° C and a second esterification tank reaction temperature of 235 ° C. The esterification catalyst ethylene glycol titanium solution having a concentration of 3 wt% was continuously and uniformly injected into the first esterification kettle at a flow rate of 41.6 kg/h; the condensation polymerization catalyst ethylene glycol solution having a concentration of 3 wt% was 41.6 kg/h. The flow rate is continuously and uniformly injected into the third compartment of the second esterification kettle. When the degree of polymerization of the esterified propylene terephthalate oligomer reaches 4, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the second at a flow rate of 2522 kg/h. The esterification kettle is produced.

The oligomer from the esterification reaction system is cooled to 220 ° C by a Sulzer-type heat exchanger and then with the modifier dipropylene glycol isophthalate-5-sulfonate solution from the in-line injection device of the modifier solution. Enter the dynamic mixer. The concentration of the dipropylene glycol isophthalate-5-sulfonic acid sodium solution is 20% by weight, the injection temperature is 110 ° C, the injection flow rate is 482 kg / h, and the dynamic viscosity is 0.05 Pa.s, wherein dipropylene glycol isophthalate - The process of injecting the sodium 5-sulfonate solution is as follows: adding the sodium dipropylene glycol isophthalate-5-sulfonate solution to the modifier solution preparation tank and preparing the solution with a concentration of 20% by weight of propylene glycol. The 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 output oligomer of the oligomer delivery metering device, and then injected into the dynamic mixer feed pipe by the modifier solution injector.

The oligomer and the modifier sodium dipropylene glycol-5-sulfonate isophthalate solution are uniformly mixed by a high-order shear mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 230 ° C. The rotational speed is 300r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 0.8, the number of stirring paddles is 2, and the length-to-diameter ratio of the vertical flat-flow reactor is 4, the falling film unit The number is 10 layers, and the diameter of the vertical full mixed reaction reactor is twice the diameter of the vertical flat flow reactor. , oligomer and modifier dipropylene glycol isophthalate-5-sulfonic acid sodium solution blend in the exchange reaction system by transesterification reaction to obtain propylene terephthalate / dipropylene glycol isophthalate - After the sodium 5-sulfonate oligomer was directly transferred from the oligomer pump to the pre-polycondensation reaction system for pre-polycondensation reaction, the reaction temperature of the exchange reaction system was 235 ° C, and the reaction time was 30 min.

The precondensation reaction system consisted of a vertical precondensation kettle in which the temperature of the reactants in the precondensation kettle was 250 °C. When the intrinsic viscosity of the prepolymer reached 0.35 dL/g, it was continuously and stably collected from the precondensation kettle by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle in which the reaction temperature of the final polycondensation kettle was 260 °C. When the intrinsic viscosity of the final polymer reaches 1.05 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a cationic dye-dyeable polyester fiber: the fiber has a breaking strength of 2.8 cN/dtex, an elongation at break of 38%, and a dyeing uniformity of 5. The dyeing results of the fiber indicate that the modifier dipropylene glycol isophthalate-5-sulfonate The segments are evenly distributed in the main chain of the polyester molecule, so that the cationic dye-dyeable polyester structure is uniform, and the fiber dyeing has no color difference.

Example 15

A slurry prepared by blending terephthalic acid and cyclohexane dimethanol was continuously and uniformly delivered at a flow rate of 2496 kg/h to an esterification reaction consisting of a vertical first esterification kettle and a horizontal second esterification kettle. The esterification reaction was carried out in the system, the reaction temperature of the first esterification vessel was 270 ° C, and the reaction temperature of the second esterification vessel was 280 ° C. The esterification catalyst antimony trioxide having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 25 kg/h. When the polymerization degree of the esterified terephthalic acid cyclohexane dimethanol ester oligomer reaches 6, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter is continuously stabilized at a flow rate of 2080 kg/h. Ground from the esterification tank.

The oligomer from the esterification reaction system is cooled to 275 ° C in a single tube mixed heat exchanger together with the modifier polyethylene terephthalate masterbatch melt from the modifier masterbatch in-line injection unit. Into the dynamic mixer, the polyethylene terephthalate masterbatch melt injection temperature is 275 ° C, the injection flow rate is 500 kg / h, the dynamic viscosity is 300 Pa.s, of which polyethylene terephthalate mother The process of particle injection is as follows: the polyethylene terephthalate masterbatch is dried by the modifier masterbatch drying system, and the melt is passed from the screw extruder through the modifier masterbatch melt metering pump according to the oligomer. The flow ratio of the output metering device output oligomer controls the metering flow and is directly injected into the feed line of the dynamic mixer.

The oligomer and the modifier polyethylene terephthalate masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 275 ° C, The rotation speed is 2500r/min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 3, the number of stirring paddles is 5, the length-to-diameter ratio of the vertical flat-flow reactor is 8, and the number of falling film units For the 25-layer, the vertical full-flow reactor is three times the diameter of the vertical flat-flow reactor. The oligomer and modifier polyethylene terephthalate masterbatch melt blend is obtained by transesterification in an exchange reaction system to obtain cyclohexane dimethanol terephthalate / ethylene terephthalate After the alcohol ester oligomer, it is directly sent from the oligomer pump to the precondensation reaction system for pre-polycondensation reaction, wherein the reaction temperature of the exchange reaction system is 275 ° C, and the reaction time is 90 min.

The precondensation reaction system consisted of a vertical first pre-polycondensation kettle and a horizontal second pre-polycondensation kettle, wherein the first pre-condensation kettle had a reactant temperature of 280 ° C and the second pre-condensation kettle had a reactant temperature of 285 ° C. When the intrinsic viscosity of the prepolymer reaches 0.25 dL/g, it is continuously and stably collected from the second pre-polycondensation vessel by a prepolymer pump and sent to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle in which the reaction temperature of the final polycondensation kettle was 290 °C. When the intrinsic viscosity of the final polymer reaches 0.67 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a high shrinkage polyester fiber having a breaking strength of 3.2 cN/dtex, an elongation at break of 45%, and a dyeing uniformity of four. The dyeing results of the fiber indicate that the molecular block of the modifier polyethylene terephthalate is uniformly 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 prepared by blending terephthalic acid and ethylene glycol is continuously and uniformly delivered at a flow rate of 2808 kg/h to an esterification reaction system composed of a vertical first esterification kettle and a horizontal second esterification kettle for esterification. The reaction temperature was 260 ° C in the first esterification reactor and 265 ° C in the second esterification reactor. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the second esterification vessel at a flow rate of 35.9 kg/h. When the degree of polymerization of the esterified ethylene terephthalate oligomer reaches 8, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2340 kg/h. The second esterification kettle is produced.

The oligomer from the esterification reaction system is cooled to 230 ° C by a Sulzer-type heat exchanger and the modifier diethylene glycol isophthalate-5-sulfonate is injected from the in-line injection device of the modifier solution. The solution and the modifier polybutylene succinate masterbatch melt from the modifier masterbatch in-line injection device enter the dynamic mixer, the diethylene glycol isophthalate-5-sulfonic acid sodium solution 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, the dynamic viscosity is 800 Pa.s. The process of injecting diethylene glycol isophthalate-5-sulfonic acid sodium solution is as follows: adding diethylene glycol isophthalate-5-sulfonate esterification solution to the modifier solution preparation tank After being prepared with a solution of ethylene glycol to a concentration of 40% by weight, the solution is transferred to the modifier solution supply tank by the difference, and the metering flow is controlled by the modifier solution metering pump according to the flow ratio of the output oligomer of the oligomer delivery metering device. Injecting the dynamic mixer feed pipe by the modifier solution injector; the polybutylene succinate masterbatch melt injection process is: polybutylene succinate masterbatch through the modifier masterbatch drying system Drying, melting by the screw extruder, directly controlling the metering flow rate and directly injecting into the feed conduit of the dynamic mixer by the modifier masterbatch melt metering pump according to the flow ratio of the oligomer delivery metering device output oligomer.

The oligomer, the sodium diethylene isophthalate-5-sulfonate solution and the polybutylene succinate masterbatch melt are uniformly mixed by a 3-stage high-shear dynamic mixer and then enter the exchange reaction system. The exchange reaction, in which the temperature of the dynamic mixer is 230 ° C, the rotation speed is 1500 r / min, the length-to-diameter ratio of the vertical full-flow reactor of the exchange reaction system is 1, the number of the stirring paddles is 2, and the vertical flat flow reaction The length to diameter ratio of the kettle is 10, the number of layers of the falling film unit is 20, and the diameter of the vertical full mixed reactor is 1.2 times the diameter of the vertical flat flow reactor. The oligomer, the sodium diethylene isophthalate-5-sulfonate solution and the polybutylene succinate masterbatch melt blend are obtained by transesterification in the exchange reaction system to obtain terephthalic acid. After the ethylene glycol ester/butylene succinate/diethylene isophthalate-5-sulfonate ternary oligomer, it is directly transported by the oligomer pump to the precondensation reaction system for precondensation. The reaction was carried out in which the reaction temperature of the exchange reaction system was 235 ° C and the reaction time was 60 min.

The pre-polycondensation reaction system consists of a vertical first pre-polycondensation kettle and a horizontal second pre-polycondensation kettle, wherein the first pre-condensation kettle has a reactant temperature of 255 ° C and the second pre-condensation kettle has a reactant temperature of 265 ° C. When the intrinsic viscosity of the prepolymer reached 0.20 dL/g, it was continuously and stably collected from the second pre-polycondensation vessel by a prepolymer pump and sent to the final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle in which the final polycondensation kettle had a reaction temperature of 275 °C. When the intrinsic viscosity of the final polymer reaches 0.62 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a cationic dye atmospheric pressure dyeable polyester fiber: the fiber has a breaking strength of 3.4 cN/dtex, an elongation at break of 35%, and a dyeing uniformity of 5 grades. The dyeing results of the fiber indicate that the modifier isophthalate-5-sulfonate sodium segment and the polybutylene succinate segment are evenly distributed in the polyester molecular backbone, so that the cationic dye is often The pressure dyeable polyester has a uniform structure, and the fiber dyeing has no color difference.

Example 17

The oligomer and the modifier polycaprolactam masterbatch melt are uniformly mixed by a 5-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 250 ° C, the rotation speed is 3000 r / min, exchange The vertical full-flow reactor of the reaction system has a length-to-diameter ratio of 0.4, a number of stirring paddles of one set, a vertical planion flow reactor with an aspect ratio of 30, and a falling film unit of 60 layers, and a vertical full-scale The diameter of the mixed flow reactor is six times the diameter of the vertical flat flow reactor. The oligomer and modifier polycaprolactam masterbatch melt blend is obtained by an ester-amide exchange reaction in the exchange reaction system to obtain a polyethylene terephthalate/caprolactam copolymer, which is directly transported by an oligomer pump to The precondensation reaction system performs a precondensation reaction in which the reaction temperature of the exchange reaction system is 260 ° C and the reaction time is 90 min.

The fiber was a hydrophilic polyester fiber having a breaking strength of 2.7 cN/dtex, an elongation at break of 23%, and a dyeing uniformity of 4.0. The dyeing results of the fiber indicate that the molecular band of the modifier polycaprolactam is uniformly distributed in the main chain of the polyester molecule, so that the hydrophilic polyester structure is uniform, and the fiber dyeing has no color difference.

Example 18

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

The oligomer and the modifier polycaprolactam masterbatch melt are uniformly mixed by a 5-stage high-shear dynamic mixer and then exchanged into an exchange reaction system, wherein the temperature of the dynamic mixer is 250 ° C, the rotation speed is 3000 r / min, exchange The vertical full-flow reactor of the reaction system has a length-to-diameter ratio of 0.4, a number of stirring paddles of one set, a vertical planion flow reactor with a length-to-diameter ratio of 1.8, and a falling film unit of three layers, a vertical full The diameter of the mixed flow reactor was 1.02 times the diameter of the vertical flat flow reactor. The oligomer and modifier polycaprolactam masterbatch melt blend is obtained by an ester-amide exchange reaction in the exchange reaction system to obtain a polyethylene terephthalate/caprolactam copolymer, which is directly transported by an oligomer pump to The precondensation reaction system performs a precondensation reaction in which the reaction temperature of the exchange reaction system is 305 ° C and the reaction time is 8 min.

The precondensation reaction system consisted of a vertical polycondensation kettle having a reaction temperature of 270 °C. When the intrinsic viscosity of the prepolymer reached 0.09 dL/g, it was continuously and stably collected from the precondensation kettle by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consists of a horizontal final polycondensation kettle, and the reaction temperature of the final polycondensation kettle The degree is 280 ° C. When the intrinsic viscosity of the final polymer reaches 0.48 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber was a hydrophilic polyester fiber having a breaking strength of 2.5 cN/dtex, an elongation at break of 20%, and a dyeing uniformity of 4.0. The dyeing results of the fiber indicate that the molecular band of the modifier polycaprolactam is uniformly distributed in the main chain of the polyester molecule, so that the hydrophilic polyester structure is uniform, and the fiber dyeing has no color difference.

Comparative example 1

The slurry prepared by blending terephthalic acid and ethylene glycol was continuously and uniformly conveyed at a flow rate of 2964 kg/h to an esterification reaction system composed of a vertical esterification tank for esterification reaction at a reaction temperature of 265 °C. A catalyst of ethylene glycol ruthenium having a concentration of 3 wt% was continuously and uniformly injected into the esterification vessel at a flow rate of 35.9 kg/h. When the polymerization degree of the esterified ethylene terephthalate oligomer reaches 4, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably from the flow rate of 2470 kg/h. It is produced in an esterification kettle.

The oligomer from the esterification reaction system enters the pre-polycondensation reaction system together with the modifier polycaprolactam masterbatch melt from the modifier masterbatch in-line injection device for pre-polycondensation reaction, and the injection temperature of the polycaprolactam masterbatch melt is 250 ° C, injection flow rate of 125kg / h, dynamic viscosity of 180Pa.s, wherein the process of polycaprolactam masterbatch injection is: polycaprolactam masterbatch is dried by the modifier masterbatch drying system, melted by a screw extruder, passed The modifier masterbatch melt metering pump is injected directly into the oligomer conduit.

The fiber was a hydrophilic polyester fiber having a breaking strength of 2.2 cN/dtex, an elongation at break of 15%, and a dyeing uniformity of 2 grades. The dyeing results of the fiber indicate that the molecular band of the polycaprolactam of the modifier is unevenly distributed in the main chain of the polyester molecule, so that the structure of the hydrophilic polyester is poor, and the color difference of the fiber dyeing occurs.

Comparative example 2

The slurry prepared by blending terephthalic acid and ethylene glycol was continuously and uniformly conveyed at a flow rate of 2964 kg/h to an esterification reaction system consisting of a vertical esterification tank for esterification reaction at a reaction temperature of 261 °C. A catalyst of cerium acetate having a concentration of 3.5% by weight was continuously and uniformly injected into the esterification vessel at a flow rate of 41.5 kg/h. Ester phthalate When the degree of polymerization of the ethylene glycol formate oligomer reaches 4, the oligomer transport metering device composed of the oligomer pump and the oligomer flow meter continuously and stably extracts from the esterification tank at a flow rate of 2246 kg/h. .

The oligomer from the esterification reaction system enters the dynamic mixer along with the modifier diethylene glycol isophthalate-5-sulfonate solution from the in-line injection device of the modifier solution. The concentration of diethylene glycol isophthalate-5-sulfonic acid sodium solution is 25wt%, the injection temperature is 90 ° C, the injection flow rate is 186 kg / h, the dynamic viscosity is 0.1 Pa.s, and the isophthalic acid diethyl ether The process of injecting the sodium glycol-5-sulfonate solution is: adding the sodium diethylene isophthalate-5-sulfonate esterification solution to the modifier solution preparation tank and preparing the ethylene glycol to form The solution with a concentration of 25wt% is transferred to the modifier solution supply tank by the difference, and the metering flow rate of the oligomer is measured by the modifier solution metering pump according to the flow ratio of the output oligomer of the oligomer delivery metering device. Inject the dynamic mixer feed line.

The oligomer and the modifier sodium diethylene glycol isophthalate-5-sulfonate solution are uniformly mixed by a 3-stage high-shear dynamic mixer, and then enter the pre-polycondensation reaction system reaction system for pre-polycondensation reaction, wherein the dynamic The temperature of the mixer was 230 ° C and the number of revolutions was 1000 r / min. The precondensation reaction system consisted of a vertical pre-condensation kettle, wherein the temperature of the pre-condensation kettle was 260 ° C. When the intrinsic viscosity of the prepolymer reached 0.15 dL/g, it was continuously and stably collected from the pre-polycondensation vessel by a prepolymer pump and sent to a final polycondensation system for final polycondensation reaction. The final polycondensation reaction system consisted of a horizontal final polycondensation kettle in which the final polycondensation kettle had a reaction temperature of 275 °C. When the intrinsic viscosity of the final polymer reaches 0.50 dL/g, the modified polyester melt is directly conveyed to the spinning position through the melt pipe to be spun, and a modified polyester fiber is obtained.

The fiber is a cationic dye-dyeable polyester fiber: the fiber has a breaking strength of 2.3 cN/dtex, an elongation at break of 18%, and a dyeing uniformity of 3.5. The dyeing results of the fiber indicate that the modifier diethylene isophthalate-5-sulfonate sodium segment is unevenly distributed in the main chain of the polyester molecule, which makes the cationic dye-dyeable polyester structurally poor, and its fiber The coloration of the dye appears.

The modified polyester melt-spun fibers prepared in the above Examples 1 to 16 and Comparative Examples 1 to 2 were tested for performance. The test items were as follows: breaking strength (cN/dtex), test method: refer to GB/T14344-2008 Elongation at break (%), test method: refer to GB/T 14344-2008; dyeing uniformity, test method: refer to GB/T6508-2001. The test results are shown in Table 1.

	断裂强度(cN/dtex)Breaking strength (cN/dtex)	断裂伸长(％)Elongation at break (%)	染色均匀度(级)Dyeing uniformity (grade)
	断裂强度(cN/dtex)Breaking strength (cN/dtex)	断裂伸长(％)Elongation at break (%)	染色均匀度(级)Dyeing uniformity (grade)	实施例1Example 1	4.14.1	3838	5.05.0
实施例2Example 2	3.03.0	3232	4.54.5	实施例1Example 1	4.14.1	3838	5.05.0
实施例2Example 2	3.03.0	3232	4.54.5	实施例3Example 3	4.24.2	4545	4.54.5
实施例4Example 4	4.84.8	2525	4.04.0	实施例3Example 3	4.24.2	4545	4.54.5
实施例4Example 4	4.84.8	2525	4.04.0	实施例5Example 5	6.06.0	24twenty four	4.04.0
实施例6Example 6	3.23.2	5050	4.54.5	实施例5Example 5	6.06.0	24twenty four	4.04.0
实施例6Example 6	3.23.2	5050	4.54.5	实施例7Example 7	4.24.2	3232	5.05.0
实施例8Example 8	3.83.8	4242	4.54.5	实施例7Example 7	4.24.2	3232	5.05.0
实施例8Example 8	3.83.8	4242	4.54.5	实施例9Example 9	3.63.6	3535	4.54.5
实施例10Example 10	2.82.8	2525	4.54.5	实施例9Example 9	3.63.6	3535	4.54.5

实施例11Example 11	3.03.0	4.54.5	4.04.0
实施例11Example 11	3.03.0	4.54.5	4.04.0	实施例12Example 12	2.72.7	5050	4.54.5
实施例13Example 13	3.43.4	2828	5.05.0	实施例12Example 12	2.72.7	5050	4.54.5
实施例13Example 13	3.43.4	2828	5.05.0	实施例14Example 14	2.82.8	3838	5.05.0
实施例15Example 15	3.23.2	4545	4.04.0	实施例14Example 14	2.82.8	3838	5.05.0
实施例15Example 15	3.23.2	4545	4.04.0	实施例16Example 16	3.43.4	3535	5.05.0
实施例17Example 17	2.72.7	23twenty three	4.04.0	实施例16Example 16	3.43.4	3535	5.05.0
实施例17Example 17	2.72.7	23twenty three	4.04.0	实施例18Example 18	2.52.5	2020	4.04.0
对比例1Comparative example 1	2.22.2	1515	2.02.0	实施例18Example 18	2.52.5	2020	4.04.0
对比例1Comparative example 1	2.22.2	1515	2.02.0	对比例2Comparative example 2	2.32.3	1818	3.53.5

It can be seen from the data in Table 1 that the modified polyester melt-spun fiber prepared by the modified polyester production method of the present invention has a breaking strength of 2.5 to 6.0 cN/dtex and an elongation at break of 20 to 50%. The dyeing uniformity is 4 to 5 grades, not only the breaking strength and elongation at break of the fiber can meet the requirements of subsequent weaving, but also have higher dyeing uniformity than the modified polyester fiber prepared by the prior art, indicating The modified polyester fiber produced by the modified polyester production method of the present invention has higher structural uniformity.

In order to further illustrate the advantageous effects of the modified polyester production process of the present invention, the thermal properties of the modified polyester fibers of Example 1 and Comparative Example 1 of the present invention were compared by differential scanning calorimetry. Test method: Perkin Elmer's Pyris 1 differential scanning calorimeter was used to rapidly heat the sample to 280 ° C, constant temperature for 5 min to completely eliminate the heat history, then quench the sample in liquid nitrogen, and then sample from 30 °C was heated to 280 ° C at a rate of 20 ° C / min. 4 is a DSC scan curve of the modified polyester, wherein a is a DSC heating curve of the modified polyester prepared in Example 1, and b is a DSC heating curve of the modified polyester prepared in Comparative Example 1.

It can be seen from FIG. 4 that only one melting peak on the DSC heating curve of the modified polyester prepared in Example 1 has a peak value of 233.3 ° C, and two of the modified polyesters prepared in Comparative Example 1 have appeared on the DSC heating curve. The melting peaks have peaks of 203.6 ° C and 248.9 ° C, respectively, which indicates that the modified polycaprolactam segments of the modified polyester prepared in Example 1 are uniformly distributed in the polyester molecular main chain, forming a uniform structure. Polyester-polycaprolactam block copolymer. The modifier polycaprolactam in the modified polyester prepared in Comparative Example 1 exists in the form of a blend or a long-chain segment embedded in a polyester molecular chain, resulting in poor structural uniformity of the modified polyester.

The raw material formula, the esterification reaction conditions and the polycondensation reaction conditions used in the preparation of the modified polyester in the first embodiment and the comparative example 1 of the present invention are the same, and the two preparation methods are different in the preparation of the modified polyester in the first embodiment. The dynamic mixer mixing process and the exchange reaction process are introduced in the process. The high-efficiency dispersion of the modifier polycaprolactam in the polyester oligomer is achieved by the dynamic mixer mixing process, so that the subsequent exchange reaction between the modifier polycaprolactam and the polyester oligomer is close to the homogeneous reaction; The reaction step introduces the modifier polycaprolactam into the main chain of the polyester oligomer by an exchange reaction to obtain a polyester-polycaprolactam oligomer having a uniform structure, thereby ensuring the uniformity of the final polycondensation product modified polyester structure. . In addition, the first embodiment of the present invention can also be seen from Table 1. The rupture strength, elongation at break and dyeing uniformity of the modified polyester fiber were significantly better than those of the modified polyester fiber obtained in Comparative Example 1.

In order to specifically explain the advantageous effects of the exchange reaction step in the method for producing a modified polyester provided by the present invention, the properties of the modified polyester fibers obtained in Example 2 and Comparative Example 2 of the present invention were analyzed and compared. The raw material formula, the esterification reaction conditions, the polycondensation reaction conditions and the dynamic mixing conditions used in the preparation of the modified polyester of the present invention 2 and Comparative Example 2 are the same, and the difference between the two preparation methods is that the preparation of the second embodiment is modified. The exchange reaction process is introduced in the process of the polyester. The uniform distribution of the modifier diethylene isophthalate-5-sulfonate in the molecular chain of the polyester is realized by the exchange reaction process, and the benzene of the modifier is solved in the prior art production method. The problem of uneven distribution of the polyester molecular main chain caused by self-polymerization of diethylene glycol dicarboxylate-5-sulfonate. It can also be seen from Table 1 that the modified polyester fibers obtained in Example 2 of the present invention are significantly better than the modified polyester fibers obtained in Comparative Example 2 in terms of breaking strength, elongation at break, and dyeing uniformity.

The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

An exchange reaction system, characterized in that the exchange reaction system comprises:

a vertical full mixed reaction reactor (2) comprising a first material inlet (1) and a first material outlet disposed thereon;

a vertical plug flow reactor (7) comprising a second material inlet and a second material outlet (10) disposed thereon;

Wherein, the vertical full mixed reaction reactor (2) is disposed on a top wall of the vertical plug flow reactor (7), and the first material outlet is in communication with the second material inlet.
The exchange reaction system according to claim 1, characterized in that the bottom wall of the vertical full mixed flow reactor (2) is at least partially shared with the top wall of the vertical plug flow reactor (7) to form The kettle wall is shared, the first material outlet and the second material inlet are overlapped and disposed on the common kettle wall.
The exchange reaction system according to claim 2, wherein said common kettle wall has a structure in which a central portion is recessed downward with respect to said vertical full mixed flow reactor (2).
The exchange reaction system according to claim 1, wherein said vertical full mixed reaction reactor (2) and said vertical flat flow reaction reactor (7) are coaxially disposed, preferably said first material outlet And the second material inlet overlaps and is located on the axis of the vertical full mixed flow reactor (2) and the vertical plug flow reactor (7).
The exchange reaction system according to claim 1, wherein the vertical full mixed flow reactor (2) has an aspect ratio of 0.5 to 3, and the length of the vertical flat flow reactor (7) is long. The diameter ratio is 2-20, the diameter of the vertical full mixed flow reactor (2) is larger than the diameter of the vertical plug flow reactor (7); more preferably the vertical full mixed flow reactor (2) The diameter is 1.05 to 5 times the diameter of the vertical flat flow reactor (7).
The exchange reaction system according to claim 1, wherein said exchange reaction system further comprises a liquid level cascade control system, said liquid level cascade control system comprising:

a liquid level transmitter for sensing an internal liquid level of the vertical full mixed flow reactor (2), and transmitting a liquid level height signal according to the liquid level height information;

An electric regulating valve disposed on the communication line of the first material outlet of the vertical full mixed reaction kettle (2) and the first material inlet of the vertical plug flow reactor (7) for receiving the a liquid level height signal, and adjusting the opening of the electric regulating valve according to the liquid level height signal.
The exchange reaction system according to claim 1, wherein said vertical full mixed flow reactor (2) comprises a first kettle body and a stirrer, said agitator comprising:

a stirring rod (5) attached to the first kettle body and having one end extending to the inside of the first kettle body;

a plurality of stirring blades (6), which are arranged symmetrically or radially symmetrically on the stirring rod (5);

Preferably, the agitator comprises a plurality of sets of agitating paddles arranged in parallel along a direction in which the agitating rods (5) extend, each of the agitating paddles comprising a plurality of the agitating paddles (6) disposed on the same horizontal surface, Preferably, the number of sets of the stirring paddle group is 2 to 5 sets, and more preferably, each of the agitating paddles (6) in the adjacent two groups of stirring paddles is staggered.
The exchange reaction system according to claim 7, wherein said vertical full mixed flow reactor (2) further comprises a heated inner coil assembly (3), said heated inner coil assembly (3) being disposed at The first kettle body is disposed around the agitator; preferably, the heating inner coil assembly (3) includes a plurality of sets of heating inner coils arranged in a concentric manner, each of the heating inner coils being along the side The axial spiral setting of the full mixed flow reactor (2).
The exchange reaction system according to claim 1, wherein said vertical plug flow reactor (7) comprises a second kettle body and a falling film assembly disposed in said second kettle body, said lowering The membrane module comprises a plurality of layers of falling film units (12) arranged in parallel; preferably the falling film module comprises 4 to 40 layers of the falling film unit (12).
The exchange reaction system according to claim 9, wherein said falling film unit comprises:

Porous cover plate (8);

An overflow tray (9) disposed downstream of the porous cover plate (8) in a material flow direction, and an overflow port on the overflow tray (9);

Preferably, the perforated cover plate (8) has a structure with a central upwardly convex shape, and an overflow opening of the overflow tray (9) is located at the center of the overflow tray (9), more preferably The perforated cover plate (8) is a conical umbrella plate.
A modified polyester production system comprising an esterification system, a precondensation system and a final polycondensation system, characterized in that the modified polyester production system further comprises the esterification system and the installation according to the material flow sequence A modifier online addition system between the precondensation systems and the exchange reaction system of any one of claims 1 to 10.
The modified polyester production system according to claim 11, wherein the modifier online addition system comprises a modifier masterbatch in-line injection device and/or a modifier solution in-line injection device;

The modifier masterbatch online injection device comprises a modifier masterbatch drying system, a screw extruder and a modifier masterbatch melt metering pump connected in sequence;

The modifier solution in-line injection device includes a modifier solution preparation tank, a modifier solution supply tank, a modifier solution metering pump, and a modifier solution injector which are sequentially connected.
The modified polyester production system according to claim 12, wherein said modified polyester production system further comprises dynamic mixing disposed between said modifier online addition system and said exchange reaction system Preferably, the dynamic mixer is a 1 to 5 high shear dynamic mixer.
The modified polyester production system according to claim 12, wherein said modified polyester production system further comprises oligomerization disposed between said esterification system and said on-line addition system in a flow flow sequence The heat exchanger and the oligomer metering device, preferably the oligomer transport metering device comprises an oligomer pump and an oligomer flow meter disposed behind the oligomer pump.
A method for preparing a modified polyester, characterized in that the preparation method comprises the following steps:

Preparing slurry and modifier separately;

The slurry is added to the modified polyester production system according to any one of claims 11 to 14, and the modifier is added to the modified polyester production system according to any one of claims 11 to 14. An online addition system to obtain the modified polyester.
The preparation method according to claim 15, wherein a modifier having a kinetic viscosity of from 0.05 Pa.s to 1000 Pa.s is formulated in the process of formulating the modifier.
The preparation method according to claim 16, wherein

When the modified polyester production system includes the oligomer heat exchanger, the oligomer heat exchanger adjusts the temperature of the oligomer to 180 to 300 ° C;

When the modified polyester production system includes the dynamic mixer, the dynamic mixer has a rotational speed of 50 to 5000 r/min.
The preparation method according to claim 17, wherein the exchange reaction system has a reaction temperature of 180 to 300 ° C and a reaction time of 10 to 180 min.
The preparation method according to claim 18, wherein the in-line viscosity of the prepolymer melt obtained after passing through the precondensation system is from 0.10 to 0.50 dL/g; preferably after passing through the final polycondensation system. The on-line viscosity of the final polymer melt was 0.50 to 1.50 dL/g.
A modified polyester fiber product, characterized in that the modified polyester fiber product is prepared from the modified polyester fiber produced by the modified polyester fiber production system according to any one of claims 11 to 14. to make.
The modified polyester fiber product according to claim 20, wherein the modified polyester fiber product has a breaking strength of 2.5 to 6.0 cN/dtex, an elongation at break of 20 to 50%, and dyeing uniformity. It is 4 to 5 levels.