CN113481622B - Composite fiber, preparation method thereof and electronic component - Google Patents

Composite fiber, preparation method thereof and electronic component Download PDF

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CN113481622B
CN113481622B CN202110697192.6A CN202110697192A CN113481622B CN 113481622 B CN113481622 B CN 113481622B CN 202110697192 A CN202110697192 A CN 202110697192A CN 113481622 B CN113481622 B CN 113481622B
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composite fiber
treatment
spinning
pva
heat
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CN113481622A (en
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祝渊
曾少博
吕尤
杨景西
蒋文龙
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • 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

Abstract

The invention discloses a composite fiber, a preparation method thereof and an electronic element, wherein the preparation method of the composite fiber comprises the steps of mixing a biodegradable water-soluble polymer, a heat-conducting filler and a solvent to prepare a spinning solution, and spinning by adopting the spinning solution to prepare a nascent composite fiber; wherein, before spinning, molecular chain disentanglement treatment is carried out on the spinning solution; and/or, after spinning, drawing the as-spun composite fiber. Through the mode, the heat-conducting filler is added into the high-molecular matrix to construct a heat-conducting channel, molecular chain disentangling treatment is carried out on the spinning solution to improve the molecular crystallinity and the orientation degree, and/or stretching treatment is carried out on the nascent composite fiber to optimize the taking and arrangement of the heat-conducting filler in the high-molecular fiber matrix, so that the prepared composite fiber has high heat conductivity.

Description

Composite fiber, preparation method thereof and electronic component
Technical Field
The invention relates to the technical field of heat-conducting high polymer materials, in particular to a composite fiber, a preparation method thereof and an electronic element.
Background
With the rapid development of the microelectronic industry, the integration level of electronic components is increased, the heat flux density of a circuit board is continuously improved, and the requirements of various fields in the electronic industry on materials capable of realizing effective heat conduction and heat dissipation are continuously upgraded. The existing heat conducting and radiating materials cannot keep up with the development steps of the electronic industry, and the effective heat management of electronic components becomes a research hotspot. The traditional metal-based, ceramic-based and carbon-based heat conduction materials have the defects of poor corrosion resistance, poor insulating property, poor impact resistance, poor mechanical property and the like, which limit the further application of the materials in the electronic industry, so that a new heat conduction material with small volume, light weight, strong deformability, good corrosion resistance, good insulation property and good heat conduction property is urgently needed to be found.
The polymer-based fiber is expected to become a novel thermal management material suitable for the electronic industry due to the characteristics of light weight, acid and alkali resistance, easy production, good insulating property, excellent mechanical property and the like. However, the intrinsic thermal conductivity of the existing polymer fibers is generally low, which limits further application thereof in the field of electronic thermal management. Therefore, how to improve the thermal conductivity of the polymer fiber and meet the requirements of the polymer fiber in practical application becomes a problem to be solved urgently.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a composite fiber, a preparation method thereof and an electronic component.
In a first aspect of the present invention, a method for preparing a composite fiber is provided, which comprises the following steps:
s1, mixing a biodegradable water-soluble polymer, a heat-conducting filler and a solvent to prepare a spinning solution;
s2, spinning by adopting the spinning solution to prepare nascent composite fibers;
wherein, before spinning, molecular chain disentanglement treatment is carried out on the spinning solution; and/or, after spinning, drawing the nascent composite fiber.
According to the preparation method of the composite fiber, at least the following beneficial effects are achieved: the preparation method adopts biodegradable water-soluble polymer as a high molecular matrix, adds heat-conducting filler, prepares nascent composite fiber through spinning, and constructs a heat-conducting channel in the high molecular matrix through the addition of the heat-conducting filler, thereby improving the heat conductivity of the composite fiber. In addition, the thermal conductivity of the conjugate fiber can be further improved by subjecting the spinning solution to a molecular chain disentanglement treatment and/or a drawing treatment of the as-spun conjugate fiber. The method has the advantages that the crystallinity and the orientation degree of a high molecular chain can be regulated and controlled by carrying out molecular chain disentangling treatment on the spinning solution, so that the molecular entanglement degree of the high molecular chain is low, the high crystallinity is realized, the defects and the interfaces in the high molecules are reduced, the phonon scattering is further reduced, the phonon transmission efficiency is improved, and the heat conductivity of the composite fiber can be improved; orientation and arrangement of the heat-conducting filler in the polymer fiber matrix can be optimized by stretching the nascent composite fiber, the heat-conducting filler in the polymer fiber matrix is uniformly dispersed and is continuously or sectionally arranged and oriented along the axial direction of the fiber, and the polymer matrix and the heat-conducting filler are high in collaborative orientation, so that the heat conductivity of the composite fiber can be improved. Therefore, the composite fiber with high thermal conductivity can be prepared by adopting the preparation method of the composite fiber.
In some embodiments of the present invention, the molecular chain disentangling treatment is at least one selected from the group consisting of sonication, shaking, shearing, stirring, extrusion, centrifugation, debubbling, addition of boric acid; and/or the stretching treatment is at least one selected from spinneret stretching, wet stretching, normal-temperature air stretching and hot stretching. Since proper stretching can improve the thermal conductivity of the final product fiber, but excessive stretching can break the heat conduction channel constructed by the heat conduction filler and reduce the thermal conductivity of the final product fiber, the stretching treatment process needs to control a proper stretching ratio, and the stretching ratio is generally controlled to be 2-9 times.
In some embodiments of the present invention, step S1 specifically comprises: dispersing a heat-conducting filler in a solvent to obtain a first dispersion liquid; and then dispersing and dissolving the biodegradable water-soluble polymer in the first dispersion liquid to prepare the spinning solution.
In some embodiments of the present invention, before dispersing and dissolving the biodegradable water-soluble polymer in the first dispersion, the method further comprises removing impurities from the biodegradable water-soluble polymer; preferably, the impurity removal treatment comprises water washing and drying; further preferably, ultrasonic and/or vibration is used to assist the water washing during the water washing.
In some embodiments of the present invention, in step S1, the thermally conductive filler is dispersed in the solvent by means of an auxiliary dispersion treatment; the auxiliary dispersion treatment comprises at least one of adding a heat-conducting filler modified dispersing agent, ultrasonic treatment, oscillation treatment, grinding treatment and centrifugal treatment. The heat-conducting filler modified dispersant can adopt anionic surfactant and/or nonionic surfactant, wherein the anionic surfactant can specifically adopt Sodium Dodecyl Sulfate (SDS), sodium dodecyl benzene sulfonate (NaDDBS) and the like, and the nonionic surfactant can adopt at least one of polyethylene glycol octyl phenyl ether (Triton X-100), TNWDIS, TNADIS, TNEDIS and TNKDIS. The mass ratio of the heat-conducting filler modified dispersant to the heat-conducting filler is generally controlled to be (0.1-300): 100.
in some embodiments of the invention, at least one of extraction and water washing treatment is further included after the spinning and before the stretching treatment; and/or, also includes heat setting after the stretching treatment; preferably, after the heat setting, oiling and drying treatment are also included.
In some embodiments of the present invention, in step S2, wet spinning or dry-wet spinning is adopted for spinning; preferably, the coagulation bath used in the spinning process comprises at least one of saturated aqueous sodium sulfate solution, methanol, ethanol.
In some embodiments of the present invention, in step S1, the biodegradable water-soluble polymer is selected from at least one of polyvinyl alcohol, polylactic acid; and/or the heat-conducting filler is a carbon material; preferably, the carbon material is selected from at least one of carbon nanotubes, carbon fibers, graphite flakes, graphene oxide; further preferably, in step S1, the mass ratio of the heat conductive filler to the biodegradable water-soluble polymer in the spinning solution is (0.1-30): 100.
in addition, in step S1, the solvent may be at least one selected from water, dimethyl sulfoxide, and ethylene glycol.
In a second aspect of the present invention, a composite fiber is provided, which is prepared by any one of the methods for preparing the composite fiber provided by the first aspect of the present invention.
The composite fiber can be applied to the preparation of electronic components (such as chips and the like) on electronic products such as mobile phones, computers and the like, so that the third aspect of the invention provides an electronic component which is prepared from any one of the composite fibers provided by the second aspect of the invention.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a small angle X-ray diffraction pattern of the product fibers of examples 1-6 and comparative examples 1-4.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the composite fiber, and the specific process comprises the following steps:
s1, weighing 0.6g of carbon material modified dispersant TNWDIS at normal temperature, adding the mixture into 100g of DMSO solution, and stirring the mixture for 20min by using a magnetic stirrer to uniformly disperse the TNWDIS; adding 2g of Carbon Nanotubes (CNTs) of TNSM2 type, and stirring by using a magnetic stirrer to ensure that the carbon nanotubes are completely wetted by a DMSO solution of a solvent instead of floating on the water surface; then carrying out ultrasonic treatment for 5min, taking out the dispersion liquid, standing in ice water, cooling, defoaming, and continuing ultrasonic treatment for 30min in total; after the ultrasonic treatment is finished, centrifugally settling the dispersion liquid to remove undispersed agglomerated particles, wherein the centrifugal rate is 2000r/min, and the centrifugal time is 30min; after the centrifugation is finished, the upper layer liquid passes through 300-mesh filter cloth to obtain final Carbon Nano Tube (CNTs) dispersion liquid, and the final dispersion liquid is marked as a first dispersion liquid A 1 . Drying the lower precipitate to constant weight, denoted as G 1 Actual content of carbon nanotubes in the dispersion =2-G 1 。
S2, weighing 20g of PVA powder (model PVA-224, alcoholysis degree 88%, polymerization degree 2400), washing with deionized water, and then putting into an oven for drying treatment at 60 ℃ so as to wash away impurities such as sodium acetate and low molecular polymers in the raw materials; then 15g of PVA washed with water was weighed out and slowly poured into the first dispersion A prepared in step S1 in portions 1 In the preparation method, a magnetic stirrer is used for stirring while feeding so that the PVA is dispersed in the first dispersion liquid A 1 Uniformly dispersing the PVA/CNTs dispersion liquid in a 50 ℃ drying oven for 2 hours after stirring for 20min, so that the PVA is dispersed in the first dispersion liquid A 1 Fully swelling; then the temperature of the oven is adjusted to 80 ℃, and the temperature is kept for 6h, so that PVA is dispersed in the first dispersion liquid A 1 Slowly dissolving; then taking out the PVA/CNTs dispersion liquid, cooling the dispersion liquid to room temperature, measuring the viscosity of the dispersion liquid to be 31502mPa & s, then carrying out ultrasonic treatment on the dispersion liquid for 30min, disentangling the PVA macromolecular chains by virtue of the ultrasonic treatment, facilitating the PVA macromolecular chains to be straightened and oriented in the subsequent processing process, and measuring the viscosity of the dispersion liquid to be 18463mPa & s; and finally standing and defoaming for later use to obtain the CNTs/PVA spinning solution.
And S3, carrying out wet spinning on the CNTs/PVA spinning solution prepared in the step S2 at normal temperature by using a wet spinning machine, setting the speed of a metering pump to be 10r/min, using absolute ethyl alcohol for a coagulating bath, and collecting fibers subjected to the coagulating bath to obtain the CNTs/PVA nascent fibers.
S4, stretching the CNTs/PVA as-spun fibers collected in the step S3 in air at normal temperature, wherein the stretching multiple is set to be 1.5 times; then carrying out multi-pass hot stretching operation, namely one-pass hot stretching: the hot stretching multiple is 3 times, the hot stretching temperature is set to be 200 ℃, and the second hot stretching is carried out: the hot stretching multiple is 2 times, and the hot stretching temperature is 220 ℃; then carrying out heat setting operation, selecting constant tension heat setting, and setting the heat setting temperature to be 220 ℃; then drying by using a hot roller, and finally collecting finished fibers by using an unreeling machine.
Example 2
The embodiment prepares the composite fiber, and the specific process comprises the following steps:
s1, weighing 2g of TNSM2 type Carbon Nanotubes (CNTs) at normal temperature, adding the CNTs into 100g of DMSO solution, and stirring by using a magnetic stirrer to enable the carbon nanotubes to be completely wetted by the DMSO solution; then carrying out ultrasonic treatment for 5min, taking out the dispersion liquid, standing in ice water, cooling, defoaming, and continuing ultrasonic treatment for 30min in total; after the ultrasonic treatment is finished, the dispersion liquid is subjected to centrifugal sedimentation to remove undispersed agglomerated particles, the centrifugal speed is 2000r/min, and the centrifugal time is 30min; after the centrifugation is finished, the upper layer liquid passes through 300-mesh filter cloth to obtain the final Carbon Nano Tube (CNTs) dispersion liquid, and the final dispersion liquid is marked as a first dispersion liquid A 2 . Drying the lower precipitate to constant weight, denoted as G 2 Actual content of carbon nanotubes in the dispersion =2-G 2 。
S2, weighing 20g of PVA powder (model PVA-224, alcoholysis degree 88%, polymerization degree 2400), washing with deionized water, and drying at 60 ℃ in an oven to remove impurities such as sodium acetate and low molecular polymer in the raw materials; 15g of the PVA which had been washed with water were then weighed out and poured slowly in portions into the first dispersion A in step S1 2 In the preparation method, a magnetic stirrer is used for stirring while feeding so that the PVA is dispersed in the first dispersion liquid A 2 Uniformly dispersing the PVA/CNTs in the mixed solution, stirring the mixed solution for 20min, and then putting the DMSO dispersion solution of the PVA/CNTs into a 50 ℃ oven to keep the temperature for 2h to ensure that the PVA is in the first dispersion solution A 2 Medium infinite swelling; then the temperature of the oven is adjusted to 80 ℃, and the temperature is kept for 6h, so that PVA is dispersed in the first dispersion liquid A 2 Slowly dissolving; and then taking out the DMSO dispersion liquid of the PVA/CNTs, carrying out ultrasonic treatment on the DMSO dispersion liquid for 30min after the DMSO dispersion liquid is cooled to room temperature, disentangling the PVA macromolecular chains by virtue of the ultrasonic treatment, facilitating the straightening orientation of the PVA macromolecular chains in the subsequent processing process, and finally standing and defoaming for later use.
S3 is the same as step S3 in example 1.
S4, the CNTs/PVA primary fibers are used for extracting DMSO at room temperature by using methanol (100%), and other operations are the same as the step S4 in the example 1.
Example 3
The embodiment prepares the composite fiber, and the specific process comprises the following steps:
s1, weighing 0.6g of carbon material modified dispersant TNWDIS at normal temperature, adding a blending solution of 58g of dimethyl sulfoxide (DMSO) and 42mL of deionized water, and stirring for 20min by using a magnetic stirrer to uniformly disperse the TNWDIS; adding 2g of Carbon Nano Tubes (CNTs) of the type of TNSM2, and stirring by using a magnetic stirrer to ensure that the carbon nano tubes are completely wetted by the DMSO/water blending solution of the solvent instead of floating on the water surface; then carrying out ultrasonic treatment for 5min, taking out the dispersion liquid, standing in ice water, cooling, defoaming, and continuing ultrasonic treatment for 30min in total; after the ultrasonic treatment is finished, centrifugally settling the dispersion liquid to remove undispersed agglomerated particles; the centrifugation speed is 2000r/min, and the centrifugation time is 30min; after the centrifugation is finished, the upper layer liquid passes through 300 meshes of filter cloth to obtain the final Carbon Nano Tube (CNTs)The dispersion is marked as the first dispersion A 3 . Drying the lower precipitate to constant weight, denoted as G 3 Actual content of carbon nanotubes in the dispersion =2-G 3 。
S2, weighing 20g of PVA powder (model PVA-224, alcoholysis degree 88%, polymerization degree 2400), washing with deionized water, and drying at 60 ℃ in an oven to remove impurities such as sodium acetate and low molecular polymer in the raw materials; then 15g of PVA which is washed by water is weighed and slowly poured into the first dispersion liquid A prepared in the step S1 in batches 3 In the preparation method, a magnetic stirrer is used for stirring while feeding so that the PVA is dispersed in the first dispersion liquid A 3 Uniformly dispersing the PVA/CNTs dispersion liquid, stirring for 20min, and then putting the PVA/CNTs dispersion liquid into a 50 ℃ oven for heat preservation for 2h to ensure that the PVA is in the first dispersion liquid A 3 Fully swelling; then the temperature of the oven is adjusted to 80 ℃, and the temperature is kept for 6h, so that PVA is dispersed in the first dispersion liquid A 3 Slowly dissolving; then taking out the DMSO/water dispersion liquid of the PVA, and standing and defoaming the PVA after the DMSO/water dispersion liquid of the PVA is cooled to room temperature for later use.
S3 is the same as step S3 in example 1.
S4, the CNTs/PVA as-spun fibers are subjected to DMSO extraction at room temperature by using methanol (100%), and other operations are the same as those in the step S4 of the example 1.
Example 4
The embodiment prepares the composite fiber, and the specific process comprises the following steps:
s1, weighing 0.6g of carbon material modified dispersant TNWDIS at normal temperature, adding the mixture into 100g of DMSO solution, and stirring the mixture for 20min by using a magnetic stirrer to uniformly disperse the TNWDIS; adding 2g of Carbon Nanotubes (CNTs) of TNSM2 type, and stirring by using a magnetic stirrer to ensure that the carbon nanotubes are completely wetted by a dispersant DMSO solution instead of floating on the water surface; then carrying out ultrasonic treatment for 5min, taking out the dispersion liquid, standing in ice water, cooling, defoaming, and continuing ultrasonic treatment for 30min in total; after the ultrasonic treatment is finished, centrifugally settling the dispersion liquid to remove undispersed agglomerated particles, wherein the centrifugal rate is 2000r/min, and the centrifugal time is 30min; after the centrifugation is finished, the upper layer liquid passes through 300-mesh filter cloth to obtain the final Carbon Nano Tube (CNTs) dispersion liquid, and the final dispersion liquid is marked as a first dispersion liquid A 4 . Drying the lower precipitate to constant weight, denoted as G 4 Actual content of carbon nanotubes in the dispersion =2-G 4 。
S2 is the same as step S2 in example 1.
S3 is the same as step S3 in example 1.
And S4, extracting DMSO (dimethyl sulfoxide) from the CNTs/PVA nascent fibers collected in the step S3 at room temperature by using methanol (100%), and then winding on a winding machine.
Example 5
The embodiment prepares the composite fiber, and the specific process comprises the following steps:
s1, weighing 0.5g of carbon material modified dispersant sodium dodecyl benzene sulfonate (NaDDBS) at normal temperature, adding the weighed material into 100mL of deionized water, and stirring for 20min by using a magnetic stirrer to ensure that the NaDDBS is uniformly dispersed; adding 2g of Graphene Oxide (GO), and stirring by using a magnetic stirrer to ensure that the GO is completely wetted by the aqueous solution of the dispersant instead of floating on the water surface; then carrying out ultrasonic treatment for 5min, taking out the dispersion liquid, standing in ice water, cooling, defoaming, and continuing ultrasonic treatment for 30min in total; after the ultrasonic treatment is finished, centrifugally settling the dispersion liquid to remove undispersed agglomerated particles, wherein the centrifugal rate is 2000r/min, and the centrifugal time is 30min; after the centrifugation is finished, the upper layer liquid passes through 300-mesh filter cloth to obtain the final Carbon Nano Tube (CNTs) dispersion liquid, and the final dispersion liquid is marked as a first dispersion liquid A 5 . The lower layer was dried and precipitated to constant weight, denoted as G 5 Actual content of carbon nanotubes in the dispersion =2-G 5 。
S2, weighing 20g of PVA powder (model PVA-1788, alcoholysis degree 88%, polymerization degree 1700) at normal temperature, and preparing the GO/PVA spinning solution by the steps which are basically the same as the step S2 in the embodiment 1.
And S3, carrying out wet spinning on the GO/PVA spinning solution prepared in the step S2 by using a wet spinning machine at normal temperature, setting the speed of a metering pump to be 10r/min, using a saturated sodium sulfate aqueous solution for a first coagulation bath, using an unsaturated sodium sulfate aqueous solution for a second coagulation bath, and collecting fibers subjected to 2 coagulation baths to obtain the GO/PVA nascent fibers.
S4 is the same as step S4 in example 1.
Example 6
The embodiment prepares the composite fiber, and the specific process comprises the following steps:
s1, weighing 0.3g of carbon material modified dispersant Sodium Dodecyl Sulfate (SDS) at normal temperature, adding the weighed mixture into 100mL of deionized water, and stirring the mixture for 20min by using a magnetic stirrer to uniformly disperse the Sodium Dodecyl Sulfate (SDS); 1.5g of carbon fibers were added and stirred with a magnetic stirrer so that the carbon fibers were completely wetted with the aqueous dispersant solution, rather than floating on the water surface. The other operations were the same as in step S1 of example 1.
S2, weighing 20g of PVA powder (model PVA-1799, alcoholysis degree 99%, polymerization degree 1700) at normal temperature, and performing the same steps as the step S2 in the example 1 to prepare the carbon fiber/PVA spinning solution.
And S3, carrying out dry-jet wet spinning on the carbon fiber/PVA spinning solution prepared in the step S2 by using a wet spinning machine at normal temperature, setting the speed of a metering pump to be 8r/min, using a saturated sodium sulfate aqueous solution for a first coagulating bath, using an unsaturated sodium sulfate aqueous solution for a second coagulating bath, carrying out wet stretching in the second coagulating bath, setting the stretching ratio to be 1.2 times, and collecting the fibers subjected to wet stretching to obtain the carbon fiber/PVA nascent fiber.
S4, stretching the carbon fiber/PVA nascent fiber collected in the step S3 in air at normal temperature, wherein the stretching multiple is set to be 1.2 times; then carrying out multi-pass hot stretching operation, namely one-pass hot stretching: the hot stretching multiple is 3 times, the hot stretching temperature is set to be 220 ℃, and the second hot stretching is carried out: the hot stretching multiple is 2 times, and the hot stretching temperature is 230 ℃; then carrying out heat setting operation, selecting constant tension heat setting, and setting the heat setting temperature to be 230 ℃; then oiling operation is carried out, then drying treatment is carried out by using a hot roller, and finally finished fibers are collected by using an unreeling machine.
Comparative example 1
The PVA fiber is prepared by the comparative example, and the specific process comprises the following steps:
s1, weighing 20g of PVA powder (model PVA-224, alcoholysis degree 88%, polymerization degree 2400), washing with deionized water, and then putting into an oven for drying treatment at 60 ℃ so as to wash away impurities such as sodium acetate, low molecular polymers and the like in the raw materials; then weighing 15g of PVA washed by water, slowly pouring the PVA into 100g of DMSO solution in batches, using a magnetic stirrer to stir while feeding so that the PVA is uniformly dispersed in the DMSO solution, and after stirring for 20min, putting the PVA/DMSO dispersion into a 50 ℃ oven to keep the temperature for 2h so that the PVA is infinitely swelled in the DMSO solution; and then adjusting the temperature of the oven to 80 ℃, and keeping the temperature for 6 hours to slowly dissolve the PVA in the DMSO solution to obtain the PVA/DMSO spinning solution.
And S2, carrying out wet spinning on the PVA/DMSO spinning solution prepared in the S1 at normal temperature by using a wet spinning machine, setting the speed of a metering pump to be 10r/min, using absolute ethyl alcohol for a coagulating bath, collecting fibers subjected to the coagulating bath to be called PVA nascent fibers, and collecting the PVA nascent fibers by using an unreeling machine.
Comparative example 2
The PVA fiber is prepared by the comparative example, and the specific process comprises the following steps:
s1, weighing 20g of PVA powder (model PVA-224, alcoholysis degree 88%, polymerization degree 2400), washing with deionized water, and drying at 60 ℃ in an oven to remove impurities such as sodium acetate and low molecular polymer in the raw materials; then weighing 15g of PVA washed by water, slowly pouring the PVA into 85mL of deionized water in batches, using a magnetic stirrer to stir while feeding so as to uniformly disperse the PVA in the water, and after stirring for 20min, putting the PVA water dispersion into a 50 ℃ oven to keep the temperature for 2h so as to fully swell the PVA in the water; then, adjusting the temperature of the oven to 80 ℃, and preserving the heat for 6 hours to ensure that the PVA is slowly dissolved in the water; and then taking out the PVA water dispersion, carrying out ultrasonic treatment on the PVA water dispersion for 30min after the PVA water dispersion is cooled to room temperature, disentangling the PVA macromolecular chains by virtue of the ultrasonic treatment, facilitating the PVA macromolecular chains to be straightened and oriented in the subsequent processing process, and finally standing and defoaming for later use.
And S2, carrying out wet spinning on the PVA spinning solution prepared in the step S1 at normal temperature by using a wet spinning machine, setting the speed of a metering pump to be 10r/min, using absolute ethyl alcohol for a coagulating bath, and collecting fibers subjected to the coagulating bath to be called PVA nascent fibers.
S3, stretching the PVA nascent fiber collected in the step S2 in air at normal temperature, wherein the stretching multiple is set to be 1.5 times; then carrying out multi-pass hot stretching operation, namely one-pass hot stretching: the hot stretching multiple is 3 times, the hot stretching temperature is set to be 200 ℃, and the second hot stretching is carried out: the hot stretching multiple is 2 times, and the hot stretching temperature is 220 ℃; then carrying out heat setting operation, selecting constant tension heat setting, and setting the heat setting temperature to be 220 ℃; then drying by using a hot roller, and finally collecting finished fibers by using an unreeling machine.
Comparative example 3
The PVA fiber is prepared by the comparative example, and the specific process comprises the following steps:
s1, weighing 20g of PVA powder (model PVA-224, alcoholysis degree 88%, polymerization degree 2400), washing with deionized water, and drying at 60 ℃ in an oven to remove impurities such as sodium acetate and low molecular polymer in the raw materials; then weighing 15g of PVA washed by water, slowly pouring the PVA into 100g of DMSO solution in batches, using a magnetic stirrer to stir while feeding so that the PVA is uniformly dispersed in the DMSO, and after stirring for 20min, putting the PVA/DMSO dispersion into a 50 ℃ oven to keep the temperature for 2h so that the PVA is fully swelled in the DMSO; then, adjusting the temperature of the oven to 80 ℃, and preserving the heat for 6 hours to ensure that the PVA is slowly dissolved in the DMSO; and then taking out the PVA/DMSO dispersion liquid, carrying out ultrasonic treatment on the PVA/DMSO dispersion liquid for 30min after the PVA/DMSO dispersion liquid is cooled to room temperature, disentangling the macromolecular chains of the PVA by virtue of the ultrasonic treatment, facilitating the macromolecular chains to be straightened and oriented in the subsequent processing process, and finally standing and defoaming for later use.
S2, the same as step S2 in comparative example 2.
S3, the same as the step S3 in the comparative example 2.
Comparative example 4
The comparative example prepares a composite fiber, and the specific process comprises the following steps:
s1, weighing 0.6g of carbon material modified dispersant TNWDIS at normal temperature, adding the mixture into 100g of DMSO solution, and stirring the mixture for 20min by using a magnetic stirrer to uniformly disperse the TNWDIS; adding 2g of Carbon Nanotubes (CNTs) of TNSM2 type, and stirring by using a magnetic stirrer to ensure that the carbon nanotubes are completely wetted by a DMSO solution of a solvent instead of floating on the water surface; then carrying out ultrasonic treatment for 5min, taking out the dispersion liquid, standing in ice water, cooling, defoaming, and continuing ultrasonic treatment for 30min in total; after the ultrasonic treatment is finished, centrifugally settling the dispersion liquid to remove undispersed agglomerated particles, wherein the centrifugal rate is 2000r/min, and the centrifugal time is 30min; and after the centrifugation is finished, enabling the upper-layer liquid to pass through 300-mesh filter cloth to obtain a final Carbon Nanotube (CNTs) dispersion liquid, and marking as a first dispersion liquid A1. And drying the lower layer precipitate until the weight is constant, marking as G1, and the actual content of the carbon nano tubes in the dispersion liquid is =2-G1.
S2, weighing 20g of PVA powder (model PVA-224, alcoholysis degree 88%, polymerization degree 2400), washing with deionized water, and drying at 60 ℃ in an oven to remove impurities such as sodium acetate and low molecular polymer in the raw materials; then weighing 15g of PVA washed by water, slowly pouring the PVA in batches into the first dispersion liquid A1 prepared in the step S1, using a magnetic stirrer to feed and stir simultaneously so that the PVA is uniformly dispersed in the first dispersion liquid A1, after stirring for 20min, putting the PVA/CNTs dispersion liquid into a 50 ℃ oven to be kept warm for 2h so that the PVA is fully swelled in the first dispersion liquid A1; then, adjusting the temperature of the oven to 80 ℃, and preserving the heat for 6 hours to slowly dissolve the PVA in the first dispersion liquid A1; then taking out the PVA/CNTs dispersion liquid, cooling the dispersion liquid to room temperature, measuring the viscosity of the dispersion liquid to be 31502mPa & s, then carrying out ultrasonic treatment on the dispersion liquid for 30min, disentangling the PVA macromolecular chains by virtue of the ultrasonic treatment, facilitating the PVA macromolecular chains to be straightened and oriented in the subsequent processing process, and measuring the viscosity of the dispersion liquid to be 18463mPa & s; and finally standing and defoaming for later use to obtain the CNTs/PVA spinning solution.
And S3, carrying out wet spinning on the CNTs/PVA spinning solution prepared in the step S2 at normal temperature by using a wet spinning machine, setting the speed of a metering pump to be 10r/min, using absolute ethyl alcohol for a coagulating bath, and collecting fibers subjected to the coagulating bath to obtain the CNTs/PVA nascent fibers.
S4, stretching the CNTs/PVA as-spun fibers collected in the step S3 in air at normal temperature, wherein the stretching multiple is set to be 1.5 times; then carrying out multi-pass hot stretching operation, namely one-pass hot stretching: the hot stretching multiple is 3 times, the hot stretching temperature is set to be 200 ℃, and the second hot stretching is carried out: the hot stretching multiple is 3 times, and the hot stretching temperature is 220 ℃; then carrying out heat setting operation, selecting constant tension heat setting, and setting the heat setting temperature to be 220 ℃; then drying by using a hot roller, and finally collecting finished fibers by using an unreeling machine.
Test examples
The thermal diffusivity of the finished fibers obtained in the above examples and comparative examples was measured by a flash method according to ASTM E1461, the specific heat capacity was measured by a differential scanning calorimeter, the density was measured by a density balance, and the thermal conductivity of each finished fiber was calculated according to "thermal conductivity = thermal diffusivity x specific heat capacity x density". The thermal conductivity of the finished fibers prepared in the above examples and comparative examples is shown in table 1 below:
TABLE 1 thermal conductivity of finished fibers of examples and comparative examples
Figure BDA0003128320170000101
As can be seen from table 1 above, the finished fibers of the above examples and comparative examples have good thermal conductivity, wherein, in the preparation processes of the pure PVA fibers of comparative example 2 and comparative example 3, the spinning solution is subjected to molecular chain disentanglement treatment before spinning, and the as-spun fibers are subjected to stretching treatment after spinning, so that the pure PVA fibers have high crystallinity, and the high molecular chains in the pure PVA fibers have good disentanglement orientation, so that the thermal conductivity of the pure PVA fibers prepared in comparative example 2 and comparative example 3 is far higher than that of the pure PVA fibers prepared in comparative example 1 without the above treatment. As can be seen from the comparison of examples 1, 2, 5, and 6 with comparative examples 2 and 3, the thermal conductivity of the composite fiber can be improved by adding the thermal conductive filler to the polymer matrix, which forms the thermal conductive channel in the polymer matrix; and the thermal conductivity of the composite fiber prepared by the carbon fiber as the heat-conducting filler is higher than that of the composite fiber prepared by the CNTs as the heat-conducting filler, and the thermal conductivity of the composite fiber prepared by the CNTs as the heat-conducting filler is higher than that of the composite fiber prepared by the GO as the heat-conducting filler. By comparing examples 1, 3, 5, when the dope solvent is different, the thermal conductivity of the finished fiber prepared by dissolving DMSO or water is higher. As can be seen from the results of the thermal conductivity tests of the composite fibers of comparative examples 1 to 6, the thermal conductivity of the composite fiber prepared by treating the spinning solution with a molecular chain disentanglement treatment before spinning and stretching the nascent fiber after spinning is significantly improved compared to the composite fiber prepared by treating the nascent fiber with one of the treatment methods alone.
Further, the observation and test of the product fibers obtained in each of the above examples and comparative examples were carried out by using a small angle X-ray diffractometer, and the results are shown in FIG. 1, in which (a) to (j) correspond to the small angle X-ray diffraction patterns of the product fibers obtained in examples 1 to 6 and comparative examples 1 to 4, respectively. Among them, the more concentrated the dispersion rings on the equatorial ring, the better the orientation of the polymer chains of the product fibers. By comparing example 1 and comparative example 4, which are identical except that the stretching ratio is different, wherein the stretching ratio of example 1 is 9 times, the stretching ratio of comparative example 4 is 13.5 times, and the two-dimensional wide-angle X-ray diffraction patterns of the two are shown in (a) in fig. 1 and (j) in fig. 1, the diffusion rings of comparative example 4 are found to be more concentrated, but the comparative thermal conductivity data is larger than that of example 1, which shows that the stretching ratio is too large, the thermal conductivity is not necessarily increased, and the thermal conduction channel which is originally overlapped in the composite fiber can be pulled apart. In the fiber preparation process, the spinning solution is subjected to molecular chain disentanglement treatment before spinning, and the nascent fiber is subjected to stretching treatment after spinning, so that the orientation of the high molecular chain can be improved, and the thermal conductivity of the material can be further improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (14)

1. A preparation method of composite fiber is characterized by comprising the following steps:
s1, mixing a biodegradable water-soluble polymer, a heat-conducting filler and a solvent to prepare a spinning solution; the heat conducting filler is selected from at least one of carbon nano tube and carbon fiber; the biodegradable water-soluble polymer is selected from at least one of polyvinyl alcohol and polylactic acid; the mass ratio of the heat-conducting filler to the biodegradable water-soluble polymer in the spinning solution is (0.1 to 30): 100, respectively;
s2, spinning by adopting the spinning solution to prepare nascent composite fibers;
wherein, before spinning, molecular chain disentanglement treatment is carried out on the spinning solution, and the method specifically comprises the following steps: carrying out ultrasonic treatment on the spinning solution, and then standing for defoaming; after spinning, the as-spun composite fiber is subjected to a drawing treatment having a draw ratio of 2~9.
2. The method of producing a composite fiber according to claim 1, wherein the drawing treatment is at least one selected from the group consisting of spinneret drawing, wet drawing, room-temperature air drawing, and thermal drawing.
3. The method for preparing a composite fiber according to claim 1, wherein step S1 specifically comprises: dispersing a heat-conducting filler in a solvent to obtain a first dispersion liquid; and then dispersing and dissolving the biodegradable water-soluble polymer in the first dispersion liquid to prepare the spinning solution.
4. The method of claim 3, further comprising removing impurities from the biodegradable water-soluble polymer before dispersing and dissolving the biodegradable water-soluble polymer in the first dispersion.
5. The method according to claim 4, wherein the impurity removal treatment comprises washing and drying.
6. The method for preparing the composite fiber according to claim 5, wherein ultrasonic and/or vibration-assisted water washing is adopted in the water washing process.
7. The method of producing a composite fiber according to claim 3, wherein in step S1, the thermally conductive filler is dispersed in a solvent by an auxiliary dispersion treatment; the auxiliary dispersion treatment comprises at least one of adding a heat-conducting filler modified dispersing agent, ultrasonic treatment, oscillation treatment, grinding treatment and centrifugal treatment.
8. The method of claim 7, wherein the thermally conductive filler-modifying dispersant is selected from anionic surfactants and/or nonionic surfactants.
9. The method for preparing the composite fiber according to claim 1, further comprising at least one of extraction and water washing treatment after the spinning and before the drawing treatment; and/or, further comprising heat setting after the stretching process.
10. The method for preparing the composite fiber according to claim 9, further comprising oiling and drying treatments after the heat setting.
11. The method of claim 1, wherein the step S2 is performed by wet spinning or dry-wet spinning.
12. The method of claim 11, wherein the coagulating bath used in the spinning process comprises at least one of saturated aqueous sodium sulfate solution, methanol, and ethanol.
13. A composite fiber produced by the method for producing a composite fiber according to any one of claims 1 to 12.
14. An electronic component characterized by being produced from the composite fiber according to claim 13.
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