WO2019228475A1 - Procédés de préparation de fibre de polyester modifiée par aérogel et tissu de polyester modifié par aérogel - Google Patents

Procédés de préparation de fibre de polyester modifiée par aérogel et tissu de polyester modifié par aérogel Download PDF

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Publication number
WO2019228475A1
WO2019228475A1 PCT/CN2019/089354 CN2019089354W WO2019228475A1 WO 2019228475 A1 WO2019228475 A1 WO 2019228475A1 CN 2019089354 W CN2019089354 W CN 2019089354W WO 2019228475 A1 WO2019228475 A1 WO 2019228475A1
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WIPO (PCT)
Prior art keywords
aerogel
stage
modified polyester
esterification reaction
mixing
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PCT/CN2019/089354
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English (en)
Chinese (zh)
Inventor
李光武
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弘暖纤科技（北京）有限公司
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Publication of WO2019228475A1 publication Critical patent/WO2019228475A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/11—Stirrers characterised by the configuration of the stirrers
    • B01F27/112—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/21—Mixers with rotary stirring devices in fixed receptacles; Kneaders characterised by their rotating shafts
    • B01F27/212—Construction of the shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms 
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

  • 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.
  • polyester fibers have always been the focus of research by related technical personnel.
  • aerogel is usually added to the polyester fiber.
  • Cisokaku 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.
  • 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.
  • 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.
  • a method for preparing an aerogel-modified polyester fiber 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.
  • the first stage esterification reaction stage or the second stage esterification reaction stage is introduced into the system.
  • 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.
  • 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.
  • the cycle of pulsating stirring is 10min to 30min, and the total time of pulsating stirring is 0.5 to 3h.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • the aerogel has a particle diameter of 10 nm to 100 ⁇ m 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%.
  • 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.
  • the active ingredients in the catalyst are organic antimony, organic germanium, organic tin, and organic titanium.
  • 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.
  • 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.
  • a method for preparing an aerogel-modified polyester fiber comprises the following steps: mixing a polycarboxylic acid and a polyol to obtain a mixed slurry; and sequentially performing the first mixing slurry
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 1 is a schematic structural diagram of a mixing device according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural diagram illustrating the cooperation of the stirring component and the adjustment part in FIG. 1;
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • the rotating shaft 22 has a mounting hole
  • 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.
  • the driving member 62 is disposed on the adjustment shaft 63.
  • the driving member 62 is disposed coaxially with the adjustment shaft 63.
  • 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.
  • 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.
  • the driving member 62 and the driven member 64 in this application are both bevel gears.
  • 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.
  • 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.
  • 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".
  • the angle of the blade 21 with respect to the rotation shaft 22 is 15 to 75 °.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the power unit 32 is a screw pump.
  • the 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.
  • 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.
  • 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.
  • 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.
  • the vibration component 10 is a variable frequency vibration rod.
  • the aerogel has a particle diameter of 10 nm to 100 ⁇ m 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 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.
  • 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.
  • a catalyst is simultaneously added to the system to obtain a mixed slurry;
  • the active ingredient in the catalyst is organic
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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
  • the residence time is 1.5h.
  • 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.
  • the aerogel (the aerogel particle size is between 80 to 100 ⁇ m 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
  • the thermal conductivity of the modified polyester fabric was 0.0270 W / (m ⁇ k).
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0280 W / (m ⁇ k).
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0295 W / (m ⁇ k).
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0302 W / (m ⁇ k).
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0316 W / (m ⁇ k).
  • 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.
  • the aerogel is aerogel / PET with a mass ratio of 4/96, and the aerogel (aerogel particle size is between 10 and 40 ⁇ m, and the porosity is between 60% and 99.9%. )
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0282 W / (m ⁇ k).
  • 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.
  • 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
  • the residence time is 1.5h.
  • the temperature is 286 ° C
  • 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.
  • the aerogel is aerogel / PET with a mass ratio of 3/97, and the aerogel (aerogel particle size is between 10 nm and 1 ⁇ m, and the porosity is between 40% and 60%. )
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0301 W / (m ⁇ k).
  • 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.
  • the polymer of trimethylene terephthalate reaches a certain value, it enters the preshrink reactor, and the preshrink reactor temperature is 235.
  • 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 ⁇ m, and the porosity is between 60% and 99.9%).
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0293 W / (m ⁇ k).
  • 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.
  • the polymer of butylene terephthalate reaches a certain value, it enters the pre-shrink reactor, and the pre-shrink reactor temperature is 215.
  • the aerogel is aerogel / PBT mass ratio of 3/97, and the aerogel (aerogel particle size is between 80-100 ⁇ m, and the porosity is between 50% -70% )
  • 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
  • the thermal conductivity of the modified polyester fabric was 0.0285 W / (m ⁇ k).
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des procédés de préparation d'une fibre de polyester modifiée par un aérogel et d'un tissu de polyester modifié par un aérogel. Le procédé de préparation d'une fibre de polyester modifiée par un aérogel comprend : le mélange d'un acide polycarboxylique et d'un polyol, la soumission séquentielle de la suspension mixte à une première réaction d'estérification, une seconde réaction d'estérification et une réaction de polycondensation, l'ajout d'un aérogel au système pendant l'étape de mélange de l'acide polycarboxylique et du polyol, la première étape de réaction d'estérification ou la seconde étape de réaction d'estérification, ou le mélange de l'aérogel avec la bouillie mélangée au moyen d'un dispositif de mélange entre l'étape de mélange et la première étape de réaction d'estérification, ou le mélanger de l'aérogel avec le produit de la première étape de réaction d'estérification au moyen d'un dispositif de mélange entre la première étape de réaction d'estérification et la seconde étape de réaction d'estérification, ce qui permet d'obtenir un polyester modifié par un aérogel ; et le filage du polyester modifié par un aérogel pour obtenir une fibre de polyester modifiée par un aérogel. La fibre de polyester modifiée par aérogel préparée par la présente invention présente de bonnes propriétés d'isolation thermique et une densité moindre.
PCT/CN2019/089354 2018-06-01 2019-05-30 Procédés de préparation de fibre de polyester modifiée par aérogel et tissu de polyester modifié par aérogel WO2019228475A1 (fr)

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CN109943947B (zh) * 2019-03-25 2021-04-02 常州旭荣针织印染有限公司 气凝胶轻质保暖面料及其制作方法
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