WO2019228475A1

WO2019228475A1 - Preparation methods for aerogel modified polyester fiber and aerogel modified polyester fabric

Info

Publication number: WO2019228475A1
Application number: PCT/CN2019/089354
Authority: WO
Inventors: 李光武
Original assignee: 弘暖纤科技（北京）有限公司
Priority date: 2018-06-01
Filing date: 2019-05-30
Publication date: 2019-12-05
Also published as: CN108715632A; CN108715632B

Abstract

The present invention provides preparation methods for an aerogel modified polyester fiber and an aerogel modified polyester fabric. The preparation method for an aerogel modified polyester fiber comprises: mixing a polycarboxylic acid and a polyol, sequentially subjecting the mixed slurry to a first esterification reaction, a second esterification reaction and a polycondensation reaction, adding an aerogel to the system during the mixing stage of the polycarboxylic acid and the polyol, the first esterification reaction stage or the second esterification reaction stage, or mixing the aerogel with the mixed slurry by means of a mixing device between the mixing stage and the first esterification reaction stage, or mixing the aerogel with the product of the first esterification reaction stage by means of a mixing device between the first esterification reaction stage and the second esterification reaction stage, thereby obtaining an aerogel modified polyester; and spinning the aerogel-modified polyester to obtain an aerogel-modified polyester fiber. The aerogel modified polyester fiber prepared by the present invention has good thermal insulation properties and lighter density.

Description

Aerogel-modified polyester fiber and method for preparing aerogel-modified polyester fabric

Technical field

The invention relates to the technical field of textile materials, in particular to a method for preparing aerogel-modified polyester fibers and aerogel-modified polyester fabric.

Background technique

As an important type of textile materials, polyester fibers have always been the focus of research by related technical personnel. Currently, in order to improve the thermal insulation performance of the fabric and reduce the weight of the fabric, aerogel is usually added to the polyester fiber.

In Chinese patent CN106835307A, aerogel-containing polyester masterbatch is first prepared, and the masterbatch needs to be dried beforehand before it is added to the polyester main melt pipe; it is then heated by a screw and melted by a metering pump. The valve flows into the static mixer and is mixed with the fiber-grade polyester melt in the main melt pipe before spinning. However, this technology has the following disadvantages: A. The process and device are complicated. This technology first requires the preparation of aerogel-containing polyester master batches. Due to the extremely low bulk density of aerogels, it is difficult for conventional screw equipment to smoothly blend aerogels and polyester chips smoothly. And the feeding method, the structure of the screw, and the melting range of the screw all require special design, which greatly increases the manufacturing difficulty and operating cost. And special design of static mixer and high-pressure injection valve will also increase costs and increase the difficulty of process control. B. Due to the high viscosity of the fiber-grade polyester melt, it can generally reach more than 100 Pa.S. At such a high viscosity, it is difficult to achieve uniform dispersion of the aerogel in a short time by a single static mixer, which increases Although time can solve the problem of uniformity to a certain extent, it will also thermally degrade the polyester, greatly reducing its spinnability and the final performance of the final fiber and even the fabric.

Chinese patent CN 103388193 provides a technology in which aerogel powder and polymer resin chips are mixed at a certain ratio, and then masterbatch is prepared by mixing at 180-250 ° C, and the masterbatch is melt-spun to obtain a masterbatch. Sexual fabric. The main problems of this method for polyester substrates are: A. The temperature is too low. The melting point of conventional fiber-grade polyester chips is about 260 ° C, and 250 ° C is not melted at all, and blending cannot be achieved; Polyester chips after sex will not only greatly increase costs and reduce spinnability, but also cannot be promoted on existing industrial equipment. B, it is difficult to ensure that the aerogel is uniformly dispersed in the polyester matrix, which will greatly reduce the spinnability and heat insulation performance.

Chinese patent CN 106633691 provides the technology of mixing the activator, dispersant and aerogel uniformly and performing the activation treatment to obtain mixed material A; adding PET chips to the mixed material A and mixed uniformly, and dried at 120 ° C. 6 The mixed material B is obtained after 1 hour; the dried mixed material B is put into a twin-screw extruder, and granulated at a frequency of 32.5 to 35.5 Hz to obtain modified polyester master batches. The disadvantages of this technology are: A. A variety of auxiliary agents need to be added, such as toluene diisocyanate, polyvinylpyrrolidone, polydimethylsiloxane, etc. The presence of this auxiliary agent not only increases costs, but some auxiliary agents such as diisocyanate also It is easy to cause changes in molecular structure such as cross-linking, etc., resulting in reduced spinnability; B. Since it is also blended by the masterbatch method, there is also the problem of uniformity of aerogel dispersion.

Based on the above factors, it is necessary to provide a method for preparing aerogel-modified polyester fibers with lower cost, more uniform aerogel dispersion, and higher spinnability.

Summary of the Invention

The main objective of the present invention is to provide an aerogel-modified polyester fiber and a method for preparing aerogel-modified polyester fabric, so as to solve the problems of high cost and high aerogel-modified polyester fiber production in the prior art. The problem of insufficient gel dispersion and poor spinnability.

In order to achieve the above object, according to one aspect of the present invention, a method for preparing an aerogel-modified polyester fiber is provided, which includes the following steps: mixing a polycarboxylic acid and a polyol to obtain a mixed slurry; and mixing the mixed slurry The material undergoes the first stage esterification reaction, the second stage esterification reaction, and the polycondensation reaction in sequence. In the mixing stage of the polycarboxylic acid and the polyol, the first stage esterification reaction stage or the second stage esterification reaction stage is introduced into the system. Adding aerogel, or mixing the aerogel and the mixed slurry with a mixing device between the mixing stage and the first esterification reaction stage, or, during the first esterification reaction stage and the second esterification reaction, The aerogel and the product of the first-stage esterification reaction are mixed by a mixing device between the stages to obtain an aerogel-modified polyester; the aerogel-modified polyester is spun to obtain an aerogel modification Polyester.

Further, the aerogel is added to the mixing slurry in the mixing stage of the polycarboxylic acid and the polyhydric alcohol, and mixed by a pulse stirring method, and the stirring rate is 120 r / min to 500 r / min.

Further, in the process of pulsating stirring, the cycle of pulsating stirring is 10min to 30min, and the total time of pulsating stirring is 0.5 to 3h.

Further, in the step of mixing the aerogel and the mixed slurry with a mixing device between the mixing stage and the first esterification reaction stage, or in the first esterification reaction stage and the second esterification reaction stage In the step of using a mixing device to mix the aerogel with the products of the first stage esterification reaction, the mixing device used includes: a casing, including a top wall, a bottom wall, and a circumferential side connecting the top wall and the bottom wall. Wall; agitating assembly, provided in the housing, the agitating assembly includes a rotating shaft and a paddle assembly provided on the rotating shaft, and the paddle assembly includes a paddle; and an adjusting part for connecting the paddle and the rotating shaft to adjust the angle of the blade with respect to the rotating shaft .

Further, the angle of the blade with respect to the rotating shaft is 15 ° to 75 °; preferably, the rotating shaft has a mounting hole, and the adjusting part includes: an adjusting shaft provided in the mounting hole of the rotating shaft; an active member provided on the adjusting shaft; The moving part is arranged in the installation hole, and the driven part is connected with the paddle, and the driving part is meshed with the driven part, so as to convert the rotary motion of the adjusting shaft into the rotary motion of the paddle.

Further, the paddle assembly includes a plurality of paddles, the plurality of paddles are arranged at intervals along the circumferential direction of the rotating shaft, and the adjusting portion includes a plurality of followers provided in one-to-one correspondence with the plurality of paddles.

Further, the housing has an internal cavity, and a first opening and a second opening communicating with the internal cavity. The height of the first opening is higher than the height of the second opening. The mixing device further includes a return component. The return component includes: Return line, the first end of the return line extends into the housing through the first opening, and the second end of the return line extends into the internal cavity of the housing through the second opening; the power device is arranged on the return line; After the aerogel, the power in the housing is used to drive the material in the casing to flow from the second end of the return line to the first end of the return line to form a return circuit.

Further, the mixing device further includes a vibration component. One end of the vibration component penetrates into the casing through the top wall, and there is a gap between the edge of the blade and the vibration component. After the aerogel is added, the material in the casing is simultaneously processed by the vibration component. Vibration mixing.

Further, the aerogel has a particle diameter of 10 nm to 100 μm and a porosity of 40 to 99.9%; preferably, the weight percentage of the aerogel in the aerogel-modified polyester fiber is 0.1 to 5%, preferably 3 to 5%.

Further, in the step of mixing the polycarboxylic acid and the polyhydric alcohol, a catalyst is simultaneously added to the system to obtain a mixed slurry; preferably, the active ingredients in the catalyst are organic antimony, organic germanium, organic tin, and organic titanium. One or more, preferably one or more of ethylene glycol antimony, ethylene glycol titanium titanate, and tetrabutyl titanate; more preferably, the catalyst is a support formed by supporting an active ingredient on a porous support Thing.

Further, an aerogel-modified polyester in a molten state is obtained after the step of polycondensation reaction, and the step of spinning the aerogel-modified polyester includes: melting the aerogel-modified polyester in a molten state into a melt Straight spinning; or, cooling and slicing the aerogel-modified polyester in a molten state, and then melt-spinning the aerogel-modified polyester after slicing.

According to another aspect of the present invention, there is also provided a method for preparing an aerogel-modified polyester fabric, comprising the following steps: preparing the aerogel-modified polyester fiber according to the above-mentioned preparation method; The polyester fiber is made into a yarn; and the yarn is woven to obtain an aerogel-modified polyester fabric.

Applying the technical solution of the present invention, a method for preparing an aerogel-modified polyester fiber is provided, which comprises the following steps: mixing a polycarboxylic acid and a polyol to obtain a mixed slurry; and sequentially performing the first mixing slurry The esterification reaction, the second esterification reaction and the polycondensation reaction, in which aerogel is added to the system in the polycarboxylic acid and polyol mixing stage, the first stage esterification reaction stage or the second stage esterification reaction stage, or Use a mixing device to mix the aerogel and the mixed slurry between the mixing stage and the first esterification reaction stage, or use a mixing device between the first esterification reaction stage and the second esterification reaction stage Mixing the aerogel with the product of the first-stage esterification reaction to obtain an aerogel-modified polyester; and spinning the aerogel-modified polyester to obtain the aerogel-modified polyester fiber.

In the above-mentioned preparation method provided by the present invention, aerogels are used in polyester based on the characteristics of extremely high porosity, extremely low bulk density and extremely low thermal conductivity, which are based on in-situ blending methods. It is added during the polymerization process, specifically during the slurry configuration stage of the polymerization reaction monomer or during the esterification reaction stage, or by using a separate mixing device after the slurry is configured or after the first stage of the esterification reaction is completed. gel. Due to the small molecular weight, low viscosity, and high fluidity of the materials in the mixed slurry or esterification reaction system, adding aerogel at this time can effectively improve the dispersibility of the aerogel in the system. Moreover, compared with the conventional twin-screw shear blending of polyester chips and aerogels, the invention adds aerogels at the above stage, which is more conducive to maintaining the aerogel's bulk structure and its porosity and size. Less damage to the shape. In addition, by using the method provided by the present invention, it is not necessary to add a small molecule modifier such as a dispersant or a surfactant when adding aerogel, which can further prevent these agents from destroying the structure of the aerogel, and can prevent these agents from reducing the polyester Spinnability also helps reduce production costs.

In short, using the preparation method provided by the present invention to prepare aerogel-modified polyester fibers can effectively reduce production costs, improve fiber spinnability, and improve the dispersion of aerogels in the polyester matrix. The aerogel-modified polyester fiber prepared by the invention has good thermal insulation performance and lighter density.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which form a part of this application, are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and the descriptions thereof are used to explain the present invention, and do not constitute an improper limitation on the present invention. In the drawings:

FIG. 1 is a schematic structural diagram of a mixing device according to an embodiment of the present invention; and

FIG. 2 is a schematic structural diagram illustrating the cooperation of the stirring component and the adjustment part in FIG. 1; FIG.

The above drawings include the following reference signs:

10. Vibration component; 20; Stirring component; 21; Paddle blade; 22; Rotary shaft; 23; Motor; 30; Return component; 31; Return line; 32; Power unit; 33; Main control valve; 40; Housing; 50, casing; 60, adjustment section; 61, connecting shaft; 62, driving member; 63, adjusting shaft; 64, follower; 70, auxiliary control valve.

Detailed ways

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

The following further describes the present application in detail with reference to specific embodiments, which cannot be understood as limiting the scope of protection claimed by the present application.

As described in the background section, in the prior art, aerogel-modified polyester fibers are expensive to prepare, aerogels are not sufficiently uniformly dispersed, and spinnability is insufficient.

In order to solve this problem, the present invention provides a method for preparing an aerogel-modified polyester fiber, which includes the following steps: mixing a polycarboxylic acid and a polyol to obtain a mixed slurry; One stage of esterification reaction, second stage of esterification reaction and polycondensation reaction, in which the aerogel is added to the system in the mixing stage of the polycarboxylic acid and the polyol, the first stage of the esterification reaction stage or the second stage of the esterification reaction stage. Or, use a mixing device to mix the aerogel and the mixed slurry between the mixing stage and the first esterification reaction stage, or use between the first esterification reaction stage and the second esterification reaction stage The mixing device mixes the aerogel with the product of the first-stage esterification reaction to obtain an aerogel-modified polyester; and spins the aerogel-modified polyester to obtain an aerogel-modified polyester fiber.

In addition, the preparation method provided by the present invention does not require additional mixing equipment such as a twin screw, the process is simple, and the production cost can be further reduced.

In a preferred embodiment, the aerogel is added to the mixed slurry during the mixing stage of the polycarboxylic acid and the polyhydric alcohol, and mixed by means of pulse stirring, and the stirring rate is 120 r / min to 500 r / min. . Adopting such agitation method and agitation strength can not only improve the dispersion effect of the aerogel as much as possible, but also help to further reduce the small molecule polycarboxylic acid and polyol or the high shear strength to destroy the structure of the aerogel. Make the size and shape of the aerogel easier to maintain, which can further improve the heat retention and low density of the aerogel-modified polyester fiber. More preferably, in the process of pulsating stirring, the cycle of pulsating stirring is 10-30 minutes, and the total time of pulsating stirring is 0.5-3 hours.

Compared with adding aerogel in the configuration stage of mixed slurry, adding aerogel in the first stage of esterification reaction or the second stage of esterification reaction is beneficial to better maintain the micropore structure of the aerogel, thereby improving Polyester fiber's thermal insulation reduces its density. In a preferred embodiment, in the step of mixing the aerogel and the mixed slurry with a mixing device between the mixing stage and the first esterification reaction stage, or in the first esterification reaction stage and the first stage, In the step of mixing the aerogel with the product of the first-stage esterification reaction using a mixing device between the two-stage esterification reaction stages, as shown in FIG. 1, the mixing device used includes: a shell 40, a stirring assembly 20, and The adjusting portion 60 and the casing 40 include a top wall, a bottom wall, and a circumferential side wall connecting the top wall and the bottom wall; the stirring component 20 is disposed in the casing 40 and the stirring component 20 includes a rotating shaft 22 and a paddle provided on the rotating shaft 22 The blade assembly includes a blade 21; the adjusting part 60 is used to connect the blade 21 and the rotating shaft 22 to adjust the angle of the blade 21 with respect to the rotating shaft 22. In the actual mixing process, the adjusting part 60 can adjust the connection between the paddle 21 and the rotating shaft 22, and the angle between the two can be adjusted, so that a certain pressure can be applied to the aerogel in the mixture to mix it with the slurry. Or the intermediate obtained in the first esterification reaction is more thoroughly mixed.

Preferably, as shown in FIG. 2, the rotating shaft 22 has a mounting hole, and the adjusting portion 60 includes an adjusting shaft 63, a driving member 62 and a driven member 64. The adjusting shaft 63 is provided in the mounting hole of the rotating shaft 22; the driving member 62 is provided on the adjusting shaft 63; the driven member 64 is provided in the mounting hole, and the driven member 64 is connected to the paddle 21, and the driving member 62 and the driven member 64 is meshed to convert the rotary motion of the adjustment shaft 63 into the rotary motion of the blade 21.

In the present application, the driving member 62 is disposed on the adjustment shaft 63. Preferably, the driving member 62 is disposed coaxially with the adjustment shaft 63. When the adjustment shaft 63 is rotated, the driving member 62 also rotates along with the driven member 64 The driving member 62 is engaged with the driving member 62, so that the driven member 64 rotates following the driving member 62, thereby driving the blade 21 to rotate, so as to adjust the inclination of the blade 21 with respect to the rotating shaft 22.

Through the above settings, the user can adjust the inclination of the blade 21 with respect to the rotating shaft 22 as required, and the driving member 62 and the driven member 64 are engaged with each other, which makes the operation mode simple and easy to implement. Preferably, the driving member 62 and the driven member 64 in this application are both bevel gears. Specifically, the central axis of each connecting shaft 61 is perpendicular to the central axis of the adjusting shaft 63, and the central axis of each follower 64 is perpendicular to the central axis of the driving member 62. Therefore, the driving member 62 and the driven member 64 are both bevel gears, so that the rotation transmission can be realized between the mutually perpendicular adjustment shaft 63 and the connecting shaft 61, and the bevel gears that mesh with each other have a large force transmission, and the operation is relatively labor-saving.

It should be noted that the specific meaning of the above-mentioned "angle between the blade 21 and the rotating shaft 22" is as follows: take points on the upper and lower sides of the blade of the blade 21, and the two points taken are the same distance from the rotating shaft 22, The angle at which the line connecting these two points deviates from the axial extension direction of the rotating shaft 22 is the "angle between the blade 21 and the rotating shaft 22". In order to further improve the dispersion effect of the aerogel, in a preferred embodiment, the angle of the blade 21 with respect to the rotation shaft 22 is 15 to 75 °.

Further, the side wall of the casing 40 of the stirring device of the present application is provided with a horizontally opened window, so that a technician can observe the mixing situation in the stirring device in real time, and adjust the blade 21 relative to the rotating shaft 22 in real time according to the mixing situation. Inclined angle to improve mixing efficiency and save mixing time.

Preferably, the stirring assembly 20 further includes a motor 23 for driving the rotating shaft 22 to rotate, and the motor 23 is disposed outside the casing 40. More preferably, the paddle assembly includes a plurality of paddles 21, the plurality of paddles 21 are arranged at intervals along the circumferential direction of the rotating shaft 22, and the adjusting portion 60 includes a plurality of followers 64 provided in one-to-one correspondence with the plurality of paddles 21. This is beneficial to further improve the dispersion effect of the aerogel.

In a preferred embodiment, the housing 40 has an internal cavity and a first opening and a second opening communicating with the internal cavity. The height of the first opening is higher than the height of the second opening. The mixing device further includes The return flow assembly 30 includes a return flow line 31. A first end of the return flow line 31 extends into the housing 40 through a first opening, and a second end of the return flow line 31 extends into the housing 40 through a second opening. The internal cavity of the device; the power device 32 is arranged on the return line 31; after the aerogel is added, the material in the casing 40 is driven by the power device 32 to flow from the second end of the return line 31 to the return line 31 first end to form a return circuit. Under the function of the reflux component 30, the aerogel with a lighter density can be further mixed with the mixed slurry or the intermediate obtained by the first-stage esterification reaction in a reflux manner, which is beneficial to further strengthening the dispersion of the aerogel. In addition, this method has less damage to the aerogel and its pore structure is more complete, which is conducive to further improving the fiber's thermal insulation performance.

In a preferred embodiment, the mixing device further includes a vibration component 10, one end of which is penetrated into the housing 40 by the top wall, and there is a space between the edge of the blade 21 and the vibration component 10; an aerogel is added Then, the materials in the casing 40 are vibrated and mixed by using the vibration assembly 10 at the same time.

As shown in FIG. 1, in the embodiment of the present invention, the return assembly 30 further includes a main control valve 33 disposed on the return line 31. The main control valve 33 is located between the first opening and the power device 32. The main control valve 33 The on-off of the return line 31 is controlled. The above-mentioned setting structure is simple, and a technician can control the on-off of the return line 31 according to the dispersion of the aerogel, which is convenient for operation. Preferably, the power unit 32 is a screw pump.

Since the screw pump has the advantages of stable flow, insensitivity to the viscosity of the medium, and low requirements for the uniformity of the conveying medium, the use of the screw pump as the power unit 32 can make the driving force uniform, and the aerogel and mixed slurry or The intermediate obtained in the first stage of the esterification reaction can be mixed uniformly in the screw pump and returned to the internal cavity through the return line 31 to promote aerogel mixing and improve mixing efficiency.

As shown in FIG. 1, in the embodiment of the present invention, the mixing device further includes a liquid inlet pipe communicating with the casing 40 and an auxiliary control valve 70 provided on the liquid inlet pipe.

Specifically, when the mixing device performs feeding, the mixed slurry or the intermediate obtained by the first stage esterification reaction is input into the internal cavity through the second opening, and the opening and closing of the auxiliary control valve 70 controls the opening and closing of the liquid inlet pipe, and the gas The gel is added to the inner cavity through an opening provided on the top of the casing 40.

In a preferred embodiment, the mixing device further includes a vibration component 10, one end of which is penetrated into the housing 40 by the top wall, and there is a space between the edge of the blade 21 and the vibration component 10; an aerogel is added After that, the materials in the casing 40 are vibrated and mixed by using the vibration assembly 10 at the same time. The combination of multiple agitation methods, especially the combination of multiple agitation methods and reflux mixing methods, makes the aerogel more fully dispersed, and can further reduce the damage to the aerogel size structure. More preferably, the vibration component 10 is a variable frequency vibration rod.

In a preferred embodiment, the aerogel has a particle diameter of 10 nm to 100 μm and a porosity of 40 to 99.9%; preferably, the weight percentage of the aerogel in the aerogel-modified polyester fiber is 0.1. To 5%, preferably 3 to 5%. In this way, the density of the fiber is lighter, and the thermal insulation performance is better.

The specific process conditions of the above-mentioned esterification reaction can be adjusted. In a preferred embodiment, the reaction temperature of the first-stage esterification reaction is 200-278 ° C, and the reaction pressure is 0.03-0.3MPa; The reaction temperature is 220-280 ° C, and the reaction pressure is 0.2-0.6 MPa; preferably, the first-stage esterification reaction is performed under stirring conditions, and the stirring rate is 120-500 r / min; preferably, the second-stage esterification The reaction is performed under stirring conditions, and the stirring rate is 120-500 r / min.

In a preferred embodiment, the polycondensation reaction includes a pre-polycondensation reaction and a final polycondensation reaction, which are sequentially performed. The reaction temperature of the pre-polycondensation reaction is 245 to 279 ° C. and the reaction pressure is 0.001 to 0.05 MPa. The reaction temperature of the final polycondensation reaction is 275 to 290 ° C, and the reaction pressure is 10 to 200 Pa.

In order to improve the reaction efficiency of the polycarboxylic acid and the polyhydric alcohol, preferably, in the step of mixing the polycarboxylic acid and the polyhydric alcohol, a catalyst is simultaneously added to the system to obtain a mixed slurry; preferably, the active ingredient in the catalyst is organic One or more of antimony, organic germanium, organic tin, and organic titanium, preferably one or more of ethylene glycol antimony, ethylene glycol titanium titanate, and tetrabutyl titanate; more preferably, a catalyst A support formed by supporting an active ingredient on a porous support.

In a preferred embodiment, the aerogel-modified polyester in a molten state is obtained after the step of the polycondensation reaction, and the step of spinning the aerogel-modified polyester includes: The polyester is melt-spun; or, the aerogel-modified polyester in a molten state is cooled and sliced, and then the aerogel-modified polyester after the slice is melt-spun.

In the above-mentioned preparation method provided by the present invention, aerogels are used in polyester based on the characteristics of extremely high porosity, extremely low bulk density and extremely low thermal conductivity, which are based on in-situ blending methods. It is added during the polymerization process, specifically during the slurry configuration stage of the polymerization monomer or during the esterification reaction stage, or by using a separate mixing device to mix it with the mixed slurry or the intermediate obtained by the first stage esterification reaction. Mix. Since the material in the mixed slurry or the esterification reaction system has a smaller molecular weight, lower viscosity, and higher fluidity during this process, adding aerogel at this time can effectively improve the dispersibility of the aerogel in the system. Moreover, compared with the conventional twin-screw shear blending of polyester chips and aerogels, the invention adds aerogels at the above stage, which is more conducive to maintaining the aerogel's bulk structure and its porosity and size. Less damage to the shape. In addition, by using the method provided by the present invention, it is not necessary to add a small molecule modifier such as a dispersant or a surfactant when adding aerogel, which can further prevent these agents from destroying the structure of the aerogel, and can prevent these agents from reducing the polyester Spinnability also helps reduce production costs.

Therefore, using the preparation method provided by the present invention to prepare the aerogel-modified polyester fiber can effectively reduce the production cost, improve the spinnability of the fiber, and improve the dispersion of the aerogel in the polyester matrix. The aerogel-modified polyester fabric prepared by the invention has good thermal insulation performance and lighter density, and the thermal conductivity of the fabric can reach a minimum of 0.027 W / (m.K).

The beneficial effects of the present invention are further illustrated by the following examples:

Example 1

The terephthalic acid, ethylene glycol molar ratio 1: 1.12 and the stoichiometric catalyst ethylene glycol antimony were prepared into a slurry in a beating device, and the obtained slurry was continuously and uniformly delivered to the reactor, and first esterified. The reactor temperature is 265 ° C and the reaction pressure is 400KPa; the temperature of the second esterification reactor is 270 ° C and the reaction pressure is 200KPa. When the polymer of ethylene terephthalate reaches a certain value, it enters the preshrink reactor and the preshrink reactor. The temperature is 279 ° C, the pressure is 2200Pa, and the residence time is 1.5h. Then it enters the final shrinking reactor, the temperature is 285 ° C and the pressure is 100Pa. After the melt viscosity reaches the standard, it is pumped out by the melt pump, and the water-cooled casting belt is pelletized.

Among them, according to the aerogel / PET mass ratio of 5/95, the aerogel (the aerogel particle size is between 80 to 100 μm and the porosity is between 98.0% to 99.9%) is the second After the end of the stage esterification reaction stage, the intermediate product obtained from the second stage esterification reaction is added to the separately set auxiliary mixing device as shown in Figures 1 and 2 for blending. The blending time is 90 minutes, in which the blades are relative to the shaft The angle is 30 to 75 °.

The above chips were melt-spun, post-treated, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.08 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0270 W / (m · k).

Example 2

The preparation process and raw materials are the same as those in Example 1, except that the aerogel is added to the intermediate product obtained from the first-stage esterification reaction after the end of the first-stage esterification reaction stage, as shown in Figure 1 and Blending is performed in the auxiliary mixing device shown in 2 and the blending time is 90 minutes, wherein the angle of the blade with respect to the rotating shaft is 15 to 35 °.

The above chips were melt-spun, post-treated, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.08 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0280 W / (m · k).

Example 3

The preparation process and raw materials are the same as in Example 1, except that the slurry of the aerogel in the slurrying device is configured and the slurry is added to the separately set auxiliary mixing device as shown in Figures 1 and 2 Blending is performed for 90 minutes, wherein the angle of the blade with respect to the rotating shaft is 15-30 °.

The above chips were melt-spun, post-treated, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.08 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0295 W / (m · k).

Example 4

The preparation process and raw materials are the same as in Example 1, except that the aerogel is added to the reaction system of the second-stage esterification reaction in the second-stage esterification reaction stage.

The chips were melt-spun, post-treated, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.09 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0302 W / (m · k).

Example 5

The preparation process and raw materials are the same as those in Example 1, except that the aerogel is added to the mixing device to mix with terephthalic acid and ethylene glycol, and the mixing is performed by pulse stirring. The stirring rate is 500r / min, stirring time is 30min.

The above chips were melt-spun, post-processed, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.09 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0316 W / (m · k).

Example 6

The terephthalic acid, ethylene glycol molar ratio 1: 1.18 and the stoichiometric catalyst ethylene glycol antimony were formulated into a slurry in a beating device, and the obtained slurry was continuously and uniformly delivered to the reactor, and first esterified. The reactor temperature is 255 ° C and the reaction pressure is 400KPa. The second esterification reactor temperature is 265 ° C and the reaction pressure is 205KPa. When the polymer of ethylene terephthalate reaches a certain value, it enters the preshrinking reactor and the preshrinking reactor. The temperature is 277 ° C, the pressure is 2200Pa, and the residence time is 1.5h. Then, it enters the final shrink reactor, the temperature is 284 ° C, and the pressure is 105Pa. After the melt viscosity reaches the standard, it is pumped out by the melt pump, and the water-cooled casting belt is pelletized.

Among them, the aerogel is aerogel / PET with a mass ratio of 4/96, and the aerogel (aerogel particle size is between 10 and 40 μm, and the porosity is between 60% and 99.9%. ) After the end of the second esterification reaction stage, the intermediate product obtained from the second esterification reaction is added to the separately set auxiliary mixing device as shown in Figures 1 and 2, and the blending time is 70 minutes. The angle of the rotating shaft is 20 to 40 °.

The above chips were melt-spun, post-treated, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.15 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0282 W / (m · k).

Example 7

The terephthalic acid, ethylene glycol molar ratio of 1: 1.16 and the stoichiometric catalyst ethylene glycol antimony were formulated into a slurry in a beating device, and the obtained slurry was continuously and uniformly delivered to the reactor for first esterification. The reactor temperature is 254 ° C and the reaction pressure is 410KPa; the second esterification reactor temperature is 263 ° C and the reaction pressure is 210KPa. When the polymer of ethylene terephthalate reaches a certain value, it enters the preshrink reactor and the preshrink reactor. The temperature is 276 ° C, the pressure is 2205Pa, and the residence time is 1.5h. Then it enters the final shrink reactor, the temperature is 286 ° C, and the pressure is 104Pa. After the melt viscosity reaches the standard, it is pumped out by the melt pump, and the water-cooled casting belt is pelletized.

Among them, the aerogel is aerogel / PET with a mass ratio of 3/97, and the aerogel (aerogel particle size is between 10 nm and 1 μm, and the porosity is between 40% and 60%. ) After the end of the second stage of the esterification reaction stage, the intermediate product obtained from the second stage of the esterification reaction is added to the separately set auxiliary mixing device as shown in Figures 1 and 2, and the blending time is 60 minutes, where the blades are relative to The angle of the rotating shaft is 30 to 75 °.

The above chips were melt-spun, post-treated, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.21 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0301 W / (m · k).

Example 8

The terephthalic acid, propylene glycol molar ratio of 1: 1.4 and the stoichiometric catalyst ethylene glycol titanium titanate were formulated into a slurry in a beating device, and the resulting slurry was continuously and uniformly delivered to the reactor for first esterification. The reactor temperature is 240 ° C and the reaction pressure is 260KPa; the second esterification reactor temperature is 250 ° C and the reaction pressure is 160KPa. When the polymer of trimethylene terephthalate reaches a certain value, it enters the preshrink reactor, and the preshrink reactor temperature is 235. ℃, pressure 500Pa, residence time 0.5h, then enter the final shrink reactor, temperature 247 ℃, pressure 100Pa, after the melt viscosity reaches the standard, it is pumped out by the melt pump, and the water-cooled casting belt is pelletized.

Among them, the aerogel is in the second stage according to the aerogel / PTT mass ratio of 3/97 (the aerogel particle size is between 80-100 μm, and the porosity is between 60% and 99.9%). After the end of the esterification reaction stage, the intermediate product obtained from the second stage of the esterification reaction is added to the separately set auxiliary mixing device as shown in Figures 1 and 2, and the blending time is 50 minutes, in which the angle of the blade relative to the shaft is 50 ~ 75 °.

The above chips were melt-spun, post-processed, and woven to obtain polyester textiles. The density of the obtained modified polyester fibers was 1.18 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0293 W / (m · k).

Example 9

The terephthalic acid, butanediol molar ratio of 1: 1.15 and the stoichiometric titanium-based catalyst were formulated into a slurry in a beating device, and the obtained slurry was continuously and uniformly delivered to the reactor. The first esterification reactor The temperature is 240 ° C and the reaction pressure is 160KPa. The temperature of the second esterification reactor is 245 ° C and the reaction pressure is 140KPa. When the polymer of butylene terephthalate reaches a certain value, it enters the pre-shrink reactor, and the pre-shrink reactor temperature is 215. ℃, pressure 5000Pa, residence time 1.5h, then enter the final shrink reactor, temperature 245 ℃, pressure 130Pa, after the melt viscosity reaches the standard, it is pumped out by the melt pump, and the water-cooled casting belt is pelletized.

Among them, the aerogel is aerogel / PBT mass ratio of 3/97, and the aerogel (aerogel particle size is between 80-100 μm, and the porosity is between 50% -70% ) After the end of the second stage of the esterification reaction stage, the intermediate product obtained from the second stage of the esterification reaction is added to the separately set auxiliary mixing device as shown in Figures 1 and 2, and the blending time is 60 minutes, where the blades are relative to The angle of the rotating shaft is 50 to 75 °.

The above chips were melt-spun, post-treated, and woven to obtain polyester textiles. The density of the modified polyester fibers obtained was 1.19 g / cm ³ , and the thermal conductivity of the modified polyester fabric was 0.0285 W / (m · k).

From the above description, it can be seen that the foregoing embodiments of the present invention achieve the following technical effects: The use of the preparation method provided by the present invention to prepare aerogel-modified polyester fibers can effectively reduce production costs and increase the spinnability of the fibers. And improve the dispersion of the aerogel in the polyester matrix. The aerogel-modified polyester fiber prepared by the invention has good thermal insulation performance and lighter density.

The above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

A method for preparing an aerogel-modified polyester fiber, characterized in that the method includes the following steps:

Mixing a polycarboxylic acid and a polyhydric alcohol to obtain a mixed slurry;

The mixed slurry is sequentially subjected to a first-stage esterification reaction, a second-stage esterification reaction, and a polycondensation reaction, wherein in the mixing stage of the polycarboxylic acid and the polyol, the first-stage esterification reaction stage Alternatively, an aerogel is added to the system in the second-stage esterification reaction stage, or an aerogel and the mixed slurry are mixed by a mixing device between the mixing stage and the first-stage esterification reaction stage. Mixing, or mixing the aerogel and the product of the first-stage esterification reaction with a mixing device between the first-stage esterification reaction stage and the second-stage esterification reaction stage to obtain a gas Gel-modified polyester

The aerogel-modified polyester is spun to obtain the aerogel-modified polyester fiber.
The preparation method according to claim 1, wherein the aerogel is added to the mixed slurry in a mixing stage of the polycarboxylic acid and the polyhydric alcohol, and a pulse stirring method is adopted. Mixing is performed at a stirring rate of 120 r / min to 500 r / min.
The preparation method according to claim 2, wherein in the process of pulsating stirring, the cycle of pulsating stirring is 10min to 30min, and the total time of the pulsating stirring is 0.5 to 3h.
The preparation method according to any one of claims 1 to 3, wherein an aerogel and the mixed slurry are mixed by a mixing device between the mixing stage and the first-stage esterification reaction stage. In the step of mixing, or, the aerogel and the product of the first-stage esterification reaction are mixed by using a mixing device between the first-stage esterification reaction stage and the second-stage esterification reaction stage. In the step, the mixing device used includes:

A housing (40) comprising a top wall, a bottom wall and a circumferential side wall connecting the top wall and the bottom wall;

A stirring assembly (20) is disposed in the casing (40), the stirring assembly (20) includes a rotating shaft (22) and a paddle assembly provided on the rotating shaft (22), and the paddle assembly includes Paddle (21);

An adjusting portion (60) is configured to connect the paddle (21) and the rotating shaft (22) to adjust an angle of the paddle (21) relative to the rotating shaft (22).
The method according to claim 4, characterized in that the angle of the paddle (21) with respect to the rotation shaft (22) is 15 ° to 75 °; preferably, the rotation shaft (22) has a mounting hole The adjusting unit (60) includes:

The adjusting shaft (63) is arranged in the mounting hole of the rotating shaft (22);

The driving member (62) is arranged on the adjusting shaft (63);

A driven member (64) is disposed in the mounting hole, and the driven member (64) is connected to the paddle (21), and the driving member (62) and the driven member (64) The meshing connection is used to convert the rotary motion of the adjusting shaft (63) into the rotary motion of the paddle (21).
The preparation method according to claim 5, wherein the paddle assembly comprises a plurality of the paddles (21), and the plurality of paddles (21) are spaced apart along a circumferential direction of the rotating shaft (22). It is provided that the adjustment part (60) includes a plurality of the followers (64) provided in a one-to-one correspondence with a plurality of the paddles (21).
The preparation method according to claim 4, characterized in that the casing (40) has an internal cavity, a first opening and a second opening communicating with the internal cavity, and a height at which the first opening is located Above the height at which the second opening is located, the mixing device further includes a return component (30), the return component (30) comprising:

A return line (31), a first end of the return line (31) protruding into the housing (40) through the first opening, and a second end of the return line (31) by The second opening extends into the internal cavity of the casing (40);

The power device (32) is arranged on the return line (31);

After the aerogel is added, the power device (32) is used to drive the material in the casing (40) to flow from the second end of the return line (31) to the return line ( 31) at the first end to form a return circuit.
The preparation method according to claim 7, wherein the mixing device further comprises a vibration component (10), and one end of the vibration component (10) penetrates into the casing (40) by the top wall. There is a gap between the edge of the paddle (21) and the vibration component (10); after the aerogel is added, the vibration component (10) is used to The materials are mixed by vibration.
The preparation method according to any one of claims 1 to 7, wherein the aerogel has a particle diameter of 10 nm to 100 μm and a porosity of 40 to 99.9%; preferably, the aerogel is modified The weight percentage of the aerogel in the polyester fiber is 0.1 to 5%, and preferably 3 to 5%.
The preparation method according to any one of claims 1 to 7, wherein in the step of mixing the polycarboxylic acid and the polyhydric alcohol, a catalyst is simultaneously added to the system, thereby obtaining the mixed slurry. Preferably, the active ingredient in the catalyst is one or more of organic antimony, organic germanium, organic tin and organic titanium, preferably ethylene glycol antimony, ethylene glycol titanium titanate, and tetrabutyl titanate One or more of them; more preferably, the catalyst is a support formed by supporting the active ingredient on a porous support.
The preparation method according to any one of claims 1 to 7, wherein the aerogel-modified polyester in a molten state is obtained after the step of the polycondensation reaction, and the aerogel is modified The polyester spinning steps include:

Melt-spinning the aerogel-modified polyester in a molten state; or

The aerogel-modified polyester in a molten state is cooled and sliced, and then the aerogel-modified polyester after the slice is melt-spun.
A method for preparing an aerogel-modified polyester fabric, comprising the following steps:

Preparing an aerogel-modified polyester fiber according to the preparation method according to any one of claims 1 to 11;

Making the aerogel-modified polyester fiber into a yarn; and

The yarn is woven to obtain the aerogel-modified polyester fabric.