CN106498538A - The preparation method and applications of high-termal conductivity aromatic polyamide fibre - Google Patents
The preparation method and applications of high-termal conductivity aromatic polyamide fibre Download PDFInfo
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- CN106498538A CN106498538A CN201611016300.4A CN201611016300A CN106498538A CN 106498538 A CN106498538 A CN 106498538A CN 201611016300 A CN201611016300 A CN 201611016300A CN 106498538 A CN106498538 A CN 106498538A
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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
- D01F6/88—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
- D01F6/90—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 polyamides
- D01F6/905—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 polyamides of aromatic polyamides
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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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
- 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
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Abstract
A kind of preparation method of high-termal conductivity aromatic polyamide fibre, comprises the following steps：Graphene oxide is scattered in organic solvent, dispersion liquid is prepared；Under inert gas shielding, m-diaminobenzene. monomer is added in aforementioned dispersion liquid and is dissolved, system is cooled to system then temperature required；It is slowly added to part m-phthaloyl chloride under agitation again, makes solution that polycondensation reaction to occur, add alkaline matter neutralization, add remaining m-phthaloyl chloride, continues reaction to be mixed until completely, obtaining meta-aromatic polyamide resin solution；Meta-aromatic polyamide resin solution carries out spinning as spinning solution using dry-jet wet-spinning spinning technique, finally prepared high-termal conductivity aromatic polyamide fibre.The thermal diffusion coefficient of product of the present invention is high, and carbon nanomaterial and graphitic nanomaterials of interpolation etc. have friction reducing effect again, and which is used as structural reinforcement material so that the mechanical property of aramid fiber also substantially gets a promotion.
Description
Technical field
A kind of the invention belongs to field of polymer material preparing technology, more particularly to preparation side of aromatic polyamide fibre
Method and the concrete application of the product.
Background technology
The oil-free self lubrication oscillating bearing outstanding advantages such as have self-lubricating, non-maintaining and reliability high, carry, adjust as rising
The part of the critical functions such as the heart, support and rotation, its are applied more and more extensively, and being can not in the high-end equipment manufacturing such as aircraft
Or the crucial general-purpose device for lacking.
Fabric liner is fitted in oscillating bearing inside and outside as solid lubricant in oil-free self lubrication oscillating bearing
Between circle, play the effect such as vital lubrication, isolation, antifriction within the bearing, while have reducing machine power consumption, anti-impact
Hit, the function such as vibration damping (shake) and noise reduction.The quality of gasket performance determines the oscillating bearing life-span, can also directly influence self-lubricating
The carrying of oscillating bearing and reliability, are the critical materials of self-lubricating knuckle bearing.And fabric liner is with high-performance virtue
Synthetic fibre fiber and polytetrafluoroethylene fibre are material knitting molding, then impregnation sizing again.Therefore, high-performance aramid fiber is lining again
Pad key raw material, the quality of its performance are very big on the impact of whole bearing performance.
Liner can cause local mistake in the case where load is born due to being rubbed by violent during high-speed rotation
Heat.And aramid fiber material and politef are macromolecular materials, they are all the non-conductors of heat, and therefore, severe friction is made
Accumulation into heat can cause the rising of bearing temperature indirectly.Work under such conditions for a long time, the acute variation of temperature accelerates
Macromolecular material aging so that the lifetime of bearing.Therefore, the advanced bearing of future generation research of high heat conduction liner is just
Become the focus of current developed country's research.And the research of high intensity, high-termal conductivity aramid fiber also just becomes and prepares high property
The focal point of energy aramid fiber.
In the patent documentation of existing announcement, the preparation method for being related to meta-aramid fibers mainly has two kinds：One is by low
Warm solution polycondensation prepares the spinning solution of meta-aramid, then obtains fiber by wet spinning；Another kind of then be to spin
Silk stock solution is obtained in the way of dry-jet wet-spinning.No matter however, which kind of method to prepare meta-aramid fibers using, in prior art
Seldom it is related to the improvement and lifting for aramid fiber heat conductivility.
Content of the invention
The technical problem to be solved is to overcome the shortcomings of to mention and defect in background above technology, there is provided one
Plant the preparation method of the high-termal conductivity aromatic polyamide fibre for being remarkably improved meta-aramid fibers heat conductivility, and the product
A kind of concrete application of product.
For solving above-mentioned technical problem, technical scheme proposed by the present invention is a kind of high-termal conductivity aromatic polyamide fibre
Preparation method, it is characterised in that comprise the following steps：
(1) graphene oxide is scattered in organic solvent, prepares dispersion liquid；
(2) under inert gas shielding, m-diaminobenzene. (MPD) monomer is added in aforementioned dispersion liquid and is dissolved, then will
It is temperature required that system is cooled to system；It is slowly added to part m-phthaloyl chloride (IPC) again under agitation, occurs solution
Polycondensation reaction, adds alkaline matter neutralization (preferable ph is 6-8), adds remaining m-phthaloyl chloride, continues stirring anti-
Meta-aromatic polyamide resin solution should be obtained up to complete；
(3) the meta-aromatic polyamide resin solution obtained using above-mentioned steps (2) is squirted as spinning solution using dry
Spinning spinning technique carries out spinning, finally prepared high-termal conductivity aromatic polyamide fibre.
The technical scheme of the invention described above is based primarily upon following principle and thinking：We show in long-term researching and analysing, golden
The mechanism of category material conducts heat is electron transition, and so as to realize the transmission of heat, and graphene oxide composite material heat conduction is based on phonon
Thermal conduction mechanism and the heat transfer realized, for the speed of the speed of phonon thermal conduction compared with electronics heat conduction, almost in the order of magnitude
Improve, therefore, phonon thermal conduction efficiency far is higher than electronics heat transfer efficiency；However, existing most of material is all difficult to sound
How sub- heat conduction, therefore seek a kind of good phonon thermal conduction material as additive and do not reduce the mechanical property of material,
The processing cost of material is not increased substantially, and this is the technical barrier that we need to overcome；Although someone was once attempted in polyamide
Add various organic and inorganic materials in preparation, but the additive of the overwhelming majority is only intended merely to the intensity of raising product, colourity
Etc. index, it is added based on material thermal conductivity is improved, and the material for adding also tends to be difficult to reach raising
The technique effect of Fypro heat conductivity.By taking the immediate material with carbon element of graphene oxide as an example, our comparison test analysis
Show, not all material with carbon element is all the good conductor of heat, and the only high material with carbon element of crystallinity, its heat conductivity are only possible to carry
Height, and the agraphitic carbon (such as white carbon black etc.) in material with carbon element, its heat conductivility are just relatively poor, due to its poor thermal conductivity generally only
It is used as high temperature resistant heat insulation material.And we through repeatedly, exploration test and trial, finally found that and adopt graphite oxide
Alkene is used as additive so as to integrated with the preparation technology of Fypro, using in-situ polymerization technology, will aoxidize stone first
After the preprocessed technique of black alkene material, dispersion in organic solvent, is subsequently adding two amine solvents, and being slow added into diacid chloride is carried out
Polycondensation obtains logarithmic viscosity number>1.8 aramid fiber resin, then through dry-jet wet spinning process, can prepare that heat conductivity is good and power
The high-termal conductivity aromatic polyamide fibre of excellent combination property is learned, unexpected prominent effect is generated.
Above-mentioned preparation method, it is preferred that first carry out ultrasonic disperse to the graphene oxide and amination is processed, then divide
Dissipate in the organic solvent.More preferable heat conductivity will be shown first through pretreated graphene oxide.
It is further preferred that the ultrasonic disperse and amination are referred to graphene oxide is filled by ultrasound and mechanical agitation
Dispersion in organic solvent, is subsequently adding amination reagent, and 1～4h of ultrasonic disperse；Amination coupling agent is added, and is led to
Cross backflow, filtration, flushing, baking step and obtain amidized graphene oxide powder.We are by the graphite oxide to using
Alkene material carries out organic amine surface modification, it is achieved thereby that grapheme material is dispersed in resin, otherwise, Graphene material
Material is easy to reunite, and in turn results in the reduction of the resin mechanical property in spinning process doped with material with carbon element, causes indirectly to break
The generation of silk phenomenon, this is unacceptable, the generation of fracture of wire for the application products such as aviation oil-free self lubrication liner
The decline of fibrous fracture strength can be caused, during liner use, caused indirectly liner to produce scratched and shorten which and use the longevity
Life.And our the aforementioned pretreatment of graphene oxide can be solved the above problems well.
Above-mentioned preparation method, it is preferred that the amination reagent is 1,6- hexamethylene diamines, ethylenediamine or ammonia；Described
Amination coupling agent is that (HATU can especially be that (7- aoxidizes benzo three to 2- to O- BTAs-tetramethylurea hexafluorophosphate
Nitrogen azoles)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid ester)；The organic solvent can be N, N '-dimethyl Methanamide (DMF),
N-methyl ketopyrrolidine (NMP), but more preferably dimethyl acetylamide (DMAc), as we have found that the toxicity of DMAc is less, molten
Solution ability is higher, and dispersion effect is more preferably.
Above-mentioned preparation method, it is preferred that in step (2), the noble gases refer to nitrogen, the m-diaminobenzene.
Refer to that, through the refined m-diaminobenzene. of rectification under vacuum, the alkaline matter preferably uses calcium hydroxide in addition to conventional Caustic soda.
Above-mentioned preparation method, it is preferred that in step (2), the m-diaminobenzene. of interpolation is rubbed with m-phthaloyl chloride
You are than controlling 1:1.001～1:1.01；In step (2), the mass ratio of point forward and backward m-phthaloyl chloride for adding twice
Control 1:3～1:1.
Above-mentioned preparation method, it is preferred that in step (2), system is cooled to system is temperature required to refer to cooling
Arrive -10 DEG C～10 DEG C；The system start temperature ranges of the polycondensation reaction are controlled at -20 DEG C～0 DEG C.
Above-mentioned preparation method, it is preferred that in step (2), adds in alkaline matter and front polycondensation reaction time
It is controlled to 1～2h；Add in alkaline matter and the rear time for continuing stirring reaction is no less than 0.5h.
Above-mentioned preparation method, it is preferred that the dry-jet wet-spinning spinning technique in step (3) specifically includes following step
Suddenly：
Obtained spinning solution is carried out heating deaeration, through dosing pump and filter after being pressurizeed with nitrogen, by carrying
Given number and the spinneret in aperture, are entered coagulating bath in atmosphere after a segment distance and are stopped, then drawn by godet roller
Through washing and stretch in going out to boiling water bath, strand goes out after boiling water bath again through alkali cleaning and washing, then again through xeothermic stretching
And winding.It is furthermore preferred that the temperature control of the coagulating bath is at 22 DEG C -28 DEG C, in the coagulating bath time of staying be 10～
20s.It is furthermore preferred that the temperature of the boiling water bath is 90 DEG C～100 DEG C, the linear velocity for entering the godet of boiling water bath is 3m/min
～8m/min, draw ratio of the strand in boiling water bath are 2.2～2.7；The alkali cleaning is using Ca (OH)2Aqueous solution.By adopting
With the preferred dry-jet wet-spinning spinning technique, can preferably improve dispersibility of the graphene oxide composite material in aramid fiber resin,
Make the mechanical property of aramid fiber not significantly affected, but heat conductivility may be significantly lifting.
In meta-aromatic polyamide polymerization process, we are added in in-situ blending (in-situ blending) mode
Graphene oxide composite material, and the aramid fiber resin liquid containing graphene oxide composite material entered by the above-mentioned dry-jet wet-spinning technique of R. concomitans
Row spinning, and then obtain high-termal conductivity meta-aramid fibers material.In prepared by the product of the present invention, by in-situ blending side
Formula, is made graphene oxide filler just be entered between macromolecular chain with nanoscale during Polymer Synthesizing, is formed with macromolecule
Molecular level mixes, and can achieve the mix homogeneously of nanoscale, and then is remarkably improved the combination property of composite.With this kind of side
Formula is improved to the heat conductivility of meta-aromatic polyamide fiber, and this still belongs to the first time in the art.
Used as a total technology design, the present invention also provides the high-termal conductivity aromatic series that a kind of above-mentioned preparation method is obtained
The application of Fypro, in 5～10W/mK, fiber number exists the heat conductivity of the high-termal conductivity aromatic polyamide fibre
More than 2.0dtex, in more than 4.0cN/dtex, elongation at break is more than 30%, fragrant by the high-termal conductivity for fracture strength
Polyamide fiber applications are in preparation aviation oil-free self lubrication cushioning product.
Compared with prior art, the present invention adopts graphene oxide composite material to be added to meta-aramid in the way of in-situ polymerization
In resin, the heat conductivity being obviously improved is obtained in that, its mechanism is：There is graphene oxide composite material itself heat well to pass
The property led, and polymer be macromolecular compound is mainly formed with Covalent bonding together by numerous atoms or atomic group, not freely
Electronics, mainly by the random diffusive transport of phonon (the exciting unit of lattice atoms collective motion state), when phonon motion speed
When rate is invariable, the size of its mean free path depend on the geometry scattering of phonon in the material with crystal lattice structure with
And the collision scattering with other phonons.Therefore the high polymer material of ordered lattice structure has higher thermal conductivity than amorphous polymer
Rate.Just as " impurity " and " defect ", the presence of which causes sound to amorphous component and incomplete crystal structure in polymer
Son causes more thermal resistances in heat transfer process, and molecule chain vibration can similarly cause thermal resistance to the scattering of phonon, so as to lead
Cause polymer thermal conductivity low.Thermal conduction mechanism about polymer matrix composite is mainly based upon " path is theoretical ", and the theory will
The conduction process of polymer matrix composite is with conducting process phase analogy, i.e. graphene oxide filler by being dispersed in polymerization
Continuous heat conduction network is defined in thing matrix so that the evolving path resistance of phonon is substantially reduced, and this conduction of heat
Resistance is closely related with the interface of the chemical composition of filler, microstructure and filler and matrix.
Compared with prior art, it is also an advantage of the present invention that：The aramid fiber prepared using the technology is compared to tradition
Aramid fiber prepared by method, (heat conductivity especially may be up to 5 in 1～10W/m K to the thermal diffusion coefficient height of product of the present invention
～10W/m K), additionally, the carbon nanomaterial that added of the present invention and graphitic nanomaterials etc. have friction reducing effect again, which is made
For structural reinforcement material so that the mechanical property of aramid fiber also substantially gets a promotion.The enforcement of the present invention, with significant warp
Ji benefit and social benefit, can lift the safety and reliability of the high-end equipment manufacturing of China.
Specific embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
Identical.Technical term used herein is intended merely to the purpose for describing specific embodiment, is not intended to limit the present invention
Protection domain.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of preparation method of the high-termal conductivity aromatic polyamide fibre of the present invention, comprises the following steps：
(1) 2g graphene oxides are dissolved in 1h in the DMAc of 1000mL by ultrasound and mechanical agitation, then under room temperature
1, the 6- hexamethylene diamines of 3000mL are added, continues ultrasonic disperse 1h；The amination coupling agent HATU of 0.1g is subsequently adding, and is transferred to
Carry out and flow back in 60 DEG C of water-baths 6h；After completion of the reaction, product is adopted ethanol dilution, filtration, and excessive with alcohol flushing
Product is finally dried by 1,6- hexamethylene diamine；By above-mentioned pretreated graphene oxide powder by ultrasonic disperse in DMAc,
1% dispersion liquid is finally prepared.
(2) under nitrogen protection, above-mentioned dispersion liquid will be added to through refined m-diaminobenzene. (MPD) monomer of rectification under vacuum
Then system is cooled to -10 DEG C by middle dissolving, then is slowly added to the m-phthaloyl chloride of dosage 40wt% under agitation
(IPC), at -5 DEG C, solution polycondensation reacts 1h, is subsequently adding calcium hydroxide powder for the system start temperature ranges control of polycondensation reaction
End neutralization, adds the m-phthaloyl chloride of remaining dosage 60wt%, continues stirring reaction half an hour, obtains concentration 16%, ratio
The meta-aromatic polyamide resin solution of dense log viscosities 1.8dl/g；M-diaminobenzene. and the mol ratio control of m-phthaloyl chloride
Make 1:1.001.
(3) the meta-aromatic polyamide resin solution obtained using above-mentioned steps (2) is squirted as spinning solution using dry
Spinning spinning technique carries out spinning, specifically：Spinning solution obtained in above-mentioned steps (2) is first carried out heating deaeration at 60 DEG C,
With after nitrogen pressurization, through dosing pump and filter, by carrying 100 hole spinnerets of the aperture for 0.07mm, the liquid of extrusion is flowed through
25 DEG C of coagulating baths are entered after crossing 1cm air layers, 10s are stopped in coagulating bath, are then led in 95 DEG C of water-baths by godet roller
Through washing and stretching, the linear velocity for entering the godet of boiling water bath is 5m/min, and draw ratio of the strand in boiling water bath be
2.5, strand goes out after boiling water bath again through the Ca (OH) of a 0.1mol/L2Solution alkali cleaning and once wash, then again through 280
DEG C xeothermic stretching, xeothermic draw ratio are 3, are finally wound, obtain the high-termal conductivity aromatic polyamide fibre of the present embodiment.
The fiber number of the high-termal conductivity aromatic polyamide fibre that the present embodiment is prepared is 2.28dtex, and fracture strength is
4.86cN/dtex, elongation at break are 34.6%, and thermal diffusion coefficient is 6.41W/m K (heat conductivility Hot Wire Technique for Measuring).
The method of testing of above-mentioned thermal diffusion coefficient is as follows：Test instrunment is TC3000 type heat conduction coefficient testers, refers to
ASTM C1113 GB/T10297-1998 are tested.Its test philosophy is according to unsteady-state heat transfer theory, is being uniformly distributed
Fiber to be measured in place an elongated tinsel, used as hot line source, its caloric value is in unit interval and unit for this tinsel
It is a definite value in length.Under the hot line source effect, the temperature of itself and surrounding will rise, and the speed of the rate of climb will take
Certainly in the size of surrounding medium heat conductivity.If the heat conductivity of tested fiber is high, then the heat of generation will be passed quickly
Pass away, hot line temperature rise is less；Conversely, if material thermal conductivity is little, the heat of generation is distributed slowly, and hot line temperature rise is just big.Should
What method was determined is the apparent thermal conductivity of fiber, because the heat conduction of fiber has radial and axial point, therefore in order to determine this two
Tested fiber and hot line can be carried out parallel or be disposed vertically by the heat conductivity in individual direction.
Embodiment 2：
A kind of preparation method of the high-termal conductivity aromatic polyamide fibre of the present invention, comprises the following steps：
(1) 2g graphene oxides are dissolved in 1h in the DMAc of 1000mL by ultrasound and mechanical agitation, then under room temperature
1, the 6- hexamethylene diamines of 3000mL are added, continues ultrasonic disperse 1h；The amination coupling agent HATU of 0.1g is subsequently adding, and is transferred to
Carry out and flow back in 60 DEG C of water-baths 6h；After completion of the reaction, product is adopted ethanol dilution, filtration, and excessive with alcohol flushing
Product is finally dried by 1,6- hexamethylene diamine；The graphene oxide powder of above-mentioned pretreatment is passed through ultrasonic disperse in DMAc, most
1% dispersion liquid is prepared eventually.
(2) under nitrogen protection, above-mentioned dispersion liquid will be added to through refined m-diaminobenzene. (MPD) monomer of rectification under vacuum
Then system is cooled to -10 DEG C by middle dissolving, then is slowly added to the m-phthaloyl chloride of dosage 50wt% under agitation
(IPC), at -5 DEG C, solution polycondensation reacts 1.2h, is subsequently adding calcium hydroxide for the system start temperature ranges control of polycondensation reaction
Powder is neutralized, and adds remaining dosage 50wt% m-phthaloyl chloride, continues stirring reaction half an hour, obtains concentration 17%, ratio
The meta-aromatic polyamide resin solution of dense log viscosities 1.65dl/g；M-diaminobenzene. and the mol ratio control of m-phthaloyl chloride
Make 1:1.01.
(3) the meta-aromatic polyamide resin solution obtained using above-mentioned steps (2) is squirted as spinning solution using dry
Spinning spinning technique carries out spinning, specifically：Spinning solution obtained in above-mentioned steps (2) is first carried out heating deaeration at 60 DEG C,
With after nitrogen pressurization, through dosing pump and filter, by carrying 100 hole spinnerets of the aperture for 0.07mm, the liquid of extrusion is flowed through
25 DEG C of coagulating baths are entered after crossing 1cm air layers, 10s are stopped in coagulating bath, are then led in 95 DEG C of water-baths by godet roller
Through washing and stretching, the linear velocity for entering the godet of boiling water bath is 5m/min, and draw ratio of the strand in boiling water bath be
2.5, strand goes out after boiling water bath again through the Ca (OH) of a 0.1mol/L2Solution alkali cleaning and once wash, then again through 280
DEG C xeothermic stretching, xeothermic draw ratio are 3, are finally wound, obtain the high-termal conductivity aromatic polyamide fibre of the present embodiment.
The fiber number of the high-termal conductivity aromatic polyamide fibre that the present embodiment is prepared is 2.52dtex, and fracture strength is
4.41cN/dtex, elongation at break are 32.8%, and thermal diffusion coefficient is that 5.83W/m K (survey by heat conductivility Hot Wire Technique for Measuring
Method for testing with embodiment 1).
Comparative example 1：
A kind of preparation method of the high-termal conductivity aromatic polyamide fibre of the present invention, comprises the following steps：
(1) many for 2.4g wall CNTs nano materials (particle size range is controlled at 5～20 μm) are used dense HNO under room temperature3Process
48h, then after deionization washing repeatedly, is scattered in the SOCl of 480mL2With 1h in the DMAc of 30mL, and using ultrasound
Disperseed with stirring, then 70 DEG C of backflow 6h filter, and use DMAc washes cleans；Be transferred into a certain amount of 1,6- oneself two
In amine, continue ultrasound the 24h that flows back in 80 DEG C of toluene solutions；After completion of the reaction, product using ethanol dilution and is filtered, and
With alcohol flushing, finally product is dried；Amination CNTs of above-mentioned pretreatment is passed through ultrasonic disperse in DMAc, is prepared into
To 1% dispersion liquid.
(2) under nitrogen protection, above-mentioned dispersion liquid will be added to through refined m-diaminobenzene. (MPD) monomer of rectification under vacuum
Then system is cooled to -10 DEG C by middle dissolving, then is slowly added to the m-phthaloyl chloride of dosage 40wt% under agitation
(IPC), at -5 DEG C, solution polycondensation reacts 1.2h, is subsequently adding calcium hydroxide for the system start temperature ranges control of polycondensation reaction
Powder is neutralized, and adds the m-phthaloyl chloride of remaining dosage 60wt%, is continued stirring reaction half an hour, is obtained concentration
16.5%th, the meta-aromatic polyamide resin solution of logarithmic viscosity number 1.7dl/g；M-diaminobenzene. and m-phthaloyl chloride
Mol ratio is controlled 1:1.001.
(3) the meta-aromatic polyamide resin solution obtained using above-mentioned steps (2) is squirted as spinning solution using dry
Spinning spinning technique carries out spinning, specifically：Spinning solution obtained in above-mentioned steps (2) is first carried out heating deaeration at 60 DEG C,
With after nitrogen pressurization, through dosing pump and filter, by carrying 100 hole spinnerets of the aperture for 0.07mm, the liquid of extrusion is flowed through
25 DEG C of coagulating baths are entered after crossing 1cm air layers, 10s are stopped in coagulating bath, are then led in 95 DEG C of water-baths by godet roller
Through washing and stretching, the linear velocity for entering the godet of boiling water bath is 5m/min, and draw ratio of the strand in boiling water bath be
2.5, strand goes out after boiling water bath again through the Ca (OH) of a 0.1mol/L2Solution alkali cleaning and once wash, then again through 280
DEG C xeothermic stretching, xeothermic draw ratio are 3, are finally wound, obtain the high-termal conductivity aromatic polyamide fibre of the present embodiment.
The fiber number of the high-termal conductivity aromatic polyamide fibre that the present embodiment is prepared is 2.23dtex, and fracture strength is
3.62cN/dtex, elongation at break are 29.3%, and thermal diffusion coefficient is that 4.24W/m K (survey by heat conductivility Hot Wire Technique for Measuring
Method for testing with embodiment 1).
Comparative example 2：
A kind of preparation method of aromatic polyamide fibre, comprises the following steps：
(1) under nitrogen protection, will dissolve through refined m-diaminobenzene. (MPD) monomer of rectification under vacuum, then by system
- 10 DEG C are cooled to, then are slowly added to the m-phthaloyl chloride (IPC) of dosage 40wt% under agitation, solution polycondensation reacts
1.2h, is subsequently adding the neutralization of calcium hydroxide powder, adds the m-phthaloyl chloride of dosage 60wt%, continue stirring reaction half little
When, obtain the meta-aromatic polyamide resin solution of concentration 16%, logarithmic viscosity number 1.8dl/g；
(2) the meta-aromatic polyamide resin solution obtained using above-mentioned steps (1) is squirted as spinning solution using dry
Spinning spinning technique carries out spinning, specifically：Spinning solution obtained in above-mentioned steps (2) is first carried out heating deaeration at 60 DEG C,
With after nitrogen pressurization, through dosing pump and filter, by carrying 100 hole spinnerets of the aperture for 0.07mm, the liquid of extrusion is flowed through
25 DEG C of coagulating baths are entered after crossing 1cm air layers, 10s are stopped in coagulating bath, are then led in 95 DEG C of water-baths by godet roller
Through washing and stretching, the linear velocity for entering the godet of boiling water bath is 5m/min, and draw ratio of the strand in boiling water bath be
2.5, strand goes out after boiling water bath again through the Ca (OH) of a 0.1mol/L2Solution alkali cleaning and once wash, then again through 280
DEG C xeothermic stretching, xeothermic draw ratio are 3, are finally wound, obtain aromatic polyamide fibre.
The fiber number of the aromatic polyamide fibre that this comparative example is obtained is 2.37dtex, and fracture strength is 3.76cN/dtex,
Elongation at break is 32.6%, and thermal diffusion coefficient is 2.76W/m K.
Embodiments of the invention described above are compareed with the aromatic polyamide fibre without carbonaceous Nano-Materials, right
Result than testing is as shown in table 1 below：
Table 1：The embodiment of the present invention and the product contrast test result of comparative example
From above example and the data of comparative example, the present invention is led as height obtained in raw material using graphene oxide
The comprehensive advantage of hot aromatic polyamide fibre, its heat conductivity and mechanical property will be significantly better than and be not added with heat conducting nanometer material
Or add the situation of other carbonaceous materials, especially in indexs such as fiber number, fracture strength, elongation at break and thermal diffusion coefficients
On, the product of the present invention has significant advantage, obtains unexpected technique effect.The product of the invention described above completely may be used
To be applied in aviation oil-free self lubrication cushioning product.
Claims (10)
1. a kind of preparation method of high-termal conductivity aromatic polyamide fibre, it is characterised in that comprise the following steps：
(1) graphene oxide is scattered in organic solvent, prepares dispersion liquid；
(2) under inert gas shielding, m-diaminobenzene. monomer is added in aforementioned dispersion liquid and is dissolved, then system is cooled to
System is temperature required；It is slowly added to part m-phthaloyl chloride under agitation again, makes solution that polycondensation reaction to occur, add alkali
Property material neutralization, add remaining m-phthaloyl chloride, continue reaction to be mixed until completely, obtain meta-aromatic polyamides
Polyimide resin solution；
(3) the meta-aromatic polyamide resin solution obtained using above-mentioned steps (2) is spun as spinning solution using dry-jet wet-spinning
Silk technique carries out spinning, finally prepared high-termal conductivity aromatic polyamide fibre.
2. preparation method according to claim 1, it is characterised in that the graphene oxide is first carried out ultrasonic disperse and
Amination process, is redispersed in the organic solvent.
3. preparation method according to claim 2, it is characterised in that the ultrasonic disperse and amination are processed and referred to oxygen
Graphite alkene disperses in organic solvent, to be subsequently adding amination reagent by ultrasound and mechanical agitation, and ultrasonic disperse 1～
4h；Amination coupling agent is added, and amidized graphene oxide powder is obtained by backflow, filtration, flushing, baking step
End.
4. preparation method according to claim 3, it is characterised in that the amination reagent is 1,6- hexamethylene diamines, second two
Amine or ammonia；The amination coupling agent is O- BTAs-tetramethylurea hexafluorophosphate；The organic solvent is two
Methylacetamide.
5. the preparation method according to any one of claim 1-4, it is characterised in that in step (2), the inertia
Gas refers to that nitrogen, the m-diaminobenzene. refer to that, through the refined m-diaminobenzene. of rectification under vacuum, the alkaline matter refers to hydrogen-oxygen
Change calcium.
6. the preparation method according to any one of claim 1-4, it is characterised in that in step (2), between interpolation
Phenylenediamine is controlled 1 with the mol ratio of m-phthaloyl chloride:1.001～1:1.01；In step (2), point forward and backward add twice
Plus m-phthaloyl chloride mass ratio control 1:3～1:1.
7. the preparation method according to any one of claim 1-4, it is characterised in that in step (2), system is cold
But arrive temperature required the referring to of system and be cooled to -10 DEG C～10 DEG C；The system start temperature ranges of the polycondensation reaction are controlled -20
DEG C～0 DEG C；Add in alkaline matter and front polycondensation reaction time is controlled to 1～2h；Add in alkaline matter and with after continue to stir
The time for mixing reaction is no less than 0.5h.
8. the preparation method according to any one of claim 1-4, it is characterised in that dry in step (3) is squirted
Spin spinning technique and specifically include following steps：
Obtained spinning solution is carried out heating deaeration, through dosing pump and filter after being pressurizeed with nitrogen, by with specific
Number and the spinneret in aperture, are entered coagulating bath in atmosphere after a segment distance and are stopped, then led to by godet roller
Through washing and stretch in boiling water bath, strand goes out after boiling water bath again through alkali cleaning and washing, then again through xeothermic stretching and volume
Around.
9. preparation method according to claim 8, it is characterised in that the temperature control of the coagulating bath at 22 DEG C -28 DEG C,
In coagulating bath, the time of staying is 10～20s；The temperature of the boiling water bath is 90 DEG C -100 DEG C, enters the line of the godet of boiling water bath
Speed is 3m/min～8m/min, and draw ratio of the strand in boiling water bath is 2.2～2.7；The alkali cleaning is using Ca (OH)2Water
Solution.
10. the high-termal conductivity aromatic polyamide fibre that a kind of preparation method as any one of claim 1～9 is obtained
Application, it is characterised in that in 5～10W/mK, fiber number exists the heat conductivity of the high-termal conductivity aromatic polyamide fibre
More than 2.0dtex, in more than 4.0cN/dtex, elongation at break is more than 30%, fragrant by the high-termal conductivity for fracture strength
Polyamide fiber applications are in preparation aviation oil-free self lubrication cushioning product.
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