CN103255501B - The preparation method of polyimide fiber - Google Patents
The preparation method of polyimide fiber Download PDFInfo
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- CN103255501B CN103255501B CN201310213557.9A CN201310213557A CN103255501B CN 103255501 B CN103255501 B CN 103255501B CN 201310213557 A CN201310213557 A CN 201310213557A CN 103255501 B CN103255501 B CN 103255501B
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Abstract
The invention provides the preparation method of a kind of polyimide fiber, comprise the following steps: monomer dianhydride and monomer diamine are polymerized, obtain polyamic acid solution；Light stabilizer solution is mixed with polyamic acid solution, obtains polyamic acid spinning solution；Polyamic acid spinning solution spinning is obtained polyamic acid fiber；By polyamic acid fiber imidizate, obtain as-spun polyimide fibers；By as-spun polyimide fibers hot gas spring, obtain polyimide fiber；One or more in formula (I), formula (II) and formula (III) structure of described monomer dianhydride；One or more in formula (IV) and formula V structure of described monomer diamine.The present invention makes spinning solution by adding certain light stabilizer after monomer diamine and monomer dianhydride are polymerized, and after spinning, hot imidization obtains polyimide fiber so that it is have good ultra-violet resistance energy.
Description
Technical field
The present invention relates to fibre technology field, particularly relate to the preparation method of a kind of polyimide fiber.
Background technology
Polyimide fiber is a kind of new special fiber, refers to the fiber containing virtue imide ring in strand.Polyamides is sub-
Amine fiber has the advantages such as high intensity, high-modulus, high temperature resistant, fire-retardant, radioprotective, resistance to chemical attack, in atomic energy industry, space
Environment, Aero-Space, national defense construction, novel building, rapid, ocean development, sports apparatus, new forms of energy, environment produce
The field such as industry and safety device has a good application prospect.
The preparation method of existing polyimide fiber includes one-step method and two-step method two kinds, and one-step method refers to use polyamides
Imide liquor directly carries out spinning, obtains polyimide fiber after hot gas spring, and the precursor of this method spinning is without entering again
Row imidizate, technological process is short, and the polyimide fiber mechanical property obtained is high, but this method requires that polyimides gathers
Compound has solubility, and its preparation cost is the highest, is unfavorable in industrial applications, and preparation process the solvent toxicity of use relatively
High.Two-step method is diamidogen and dianhydride first to carry out polycondensation reaction generate polyamic acid stock solution, then carries out spinning and obtains polyamide
Acid fiber, then finally obtain polyimide fiber through imidizate and hot gas spring process, this method is due to low cost, suitable
Obtain a wide range of applications in industrialized developing.
Along with the development of science and technology, in spacecraft, loomage, flexible cable, nuclear industry, composite and fire prevention resistance
The polyimide fiber that the aspect such as combustible material needs also needs ultraviolet-resistant aging performance in addition to above-mentioned characteristic, but prior art
Research about this respect has no report.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the preparation method of a kind of polyimide fiber, this
The polyimide fiber that the preparation method of the polyimide fiber that invention provides prepares has UV resistant performance.
The invention provides the preparation method of a kind of polyimide fiber, comprise the following steps:
Monomer dianhydride and monomer diamine are polymerized, obtain polyamic acid solution；
Light stabilizer solution is mixed with polyamic acid solution, obtains polyamic acid spinning solution；
Polyamic acid spinning solution spinning is obtained polyamic acid fiber；
By polyamic acid fiber imidizate, obtain as-spun polyimide fibers；
By as-spun polyimide fibers hot gas spring, obtain polyimide fiber；
One or more in formula (I), formula (II) and formula (III) structure of described monomer dianhydride；
One or more in formula (IV) and formula V structure of described monomer diamine；
Preferably, described light stabilizer one in triazole, Benzophenones and hindered amine light stabilizer or
Several.
Preferably, in described light stabilizer solution solvent selected from DMF, N,N-dimethylacetamide,
One or more in dimethyl sulfoxide and N-Methyl pyrrolidone.
Preferably, described light stabilizer and described monomer dianhydride and monomer diamine and mass ratio be (0.05～5):
100。
Preferably, the mol ratio of described monomer dianhydride and monomer diamine is 1:0.8～1.5.
Preferably, in described polyamic acid solution, the mass concentration of polyamic acid is 5～35wt%.
Preferably, described polymerization temperature is-10 DEG C～50 DEG C.
Preferably, described polyamic acid spinning solution is carried out spinning and specifically includes following steps:
After the filtration of described polyamic acid spinning solution, vacuum defoamation, extruded by spinneret orifice；
Solidify entering coagulating bath by the spinneret orifice extrudate that obtains of extrusion through air layer, then through washing, dried,
Obtain polyamic acid fiber.
Preferably, described imidizate temperature is 50 DEG C～500 DEG C；Described programming rate is 1 DEG C/min～30 DEG C/min.
Preferably, the drawing temperature of described hot gas spring is 350 DEG C～550 DEG C, and the draft ratio of described hot gas spring is 1～6
Times.
Compared with prior art, the invention provides the preparation method of a kind of polyimide fiber, comprise the following steps: will
Monomer dianhydride and monomer diamine polymerization, obtain polyamic acid solution；Light stabilizer solution is mixed with polyamic acid solution, obtains
Polyamic acid spinning solution；Polyamic acid spinning solution spinning is obtained polyamic acid fiber；By polyamic acid fiber acid imide
Change, obtain as-spun polyimide fibers；By as-spun polyimide fibers hot gas spring, obtain polyimide fiber；Described monomer two
One or more in formula (I), formula (II) and formula (III) structure of acid anhydride；Described monomer diamine is selected from formula (IV) and formula V knot
One or more in structure.The present invention makes spin by adding certain light stabilizer after monomer diamine and monomer dianhydride are polymerized
Silk solution, after spinning, hot imidization obtains polyimide fiber so that polyimide fiber has good ultra-violet resistance energy；This
Invent and be polymerized by specific monomer diamine and monomer dianhydride, the mechanical property of the polyimide fiber prepared not under
Fall.The technique of the present invention is simple, can be widely applied to spacecraft, loomage, nuclear industry, composite and applied fireproofing
In field.Test result indicate that, polyimide fiber fracture strength 1.4GPa prepared by the present invention, modulus 20.9GPa, fracture is stretched
Long rate 8.32%, and irradiation after 2000 hours strength retention be 96.3%.
Detailed description of the invention
The invention provides the preparation method of a kind of polyimide fiber, comprise the following steps:
Monomer dianhydride and monomer diamine are polymerized, obtain polyamic acid solution；
Light stabilizer solution is mixed with polyamic acid solution, obtains polyamic acid spinning solution；
Polyamic acid spinning solution spinning is obtained polyamic acid fiber；
By polyamic acid fiber imidizate, obtain as-spun polyimide fibers；
By as-spun polyimide fibers hot gas spring, obtain polyimide fiber；
One or more in formula (I), formula (II) and formula (III) structure of described monomer dianhydride；
One or more in formula (IV) and formula V structure of described monomer diamine；
In the present invention, monomer dianhydride and monomer diamine are polymerized, obtain polyamic acid solution.Described monomer dianhydride is selected from
One or more in formula (I), formula (II) and formula (III) structure；
One or more in formula (IV) and formula V structure of described monomer diamine；
The present invention is not particularly limited for the source of described monomer dianhydride and monomer diamine, can be commercially available.
First monomer dianhydride and monomer diamine are dissolved post polymerization by the present invention in a solvent.Obtain polyamic acid solution.Institute
State solvent and be preferably selected from DMF, N,N-dimethylacetamide, dimethyl sulfoxide and N-Methyl pyrrolidone
In one or more.The mol ratio of described monomer dianhydride and monomer diamine is preferably 1:0.8～1.5, more preferably 1:0.95
～1.05.Described polymerization temperature is preferably-10 DEG C～50 DEG C；Described polymerization time is preferably 4h～10h.Described polyamic acid is molten
In liquid, the mass concentration of polyamic acid is preferably 5～35wt%.
After obtaining polyamic acid solution, light stabilizer solution is mixed with polyamic acid solution, obtain polyamic acid spinning
Stock solution.Be specially and light stabilizer be dissolved in solvent, add polyamic acid solution, stir, filter after obtain polyamic acid and spin
Silk stock solution.Described solvent is preferably selected from DMF, N,N-dimethylacetamide, dimethyl sulfoxide and N-first
One or more in base ketopyrrolidine.The present invention is the most unrestricted for the mode of described stirring and filtration, people in the art
Stirring known to Yuan and filter type.
In the present invention, during described light stabilizer is preferably selected from triazole, Benzophenones and hindered amine light stabilizer
One or more.Described triazole light stabilizer is preferably selected from UV-P (UV-
P), 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole (UV-327), 2-(2 '-hydroxyl-3 '-tertiary fourth
Base-5 '-aminomethyl phenyl)-5-chlorobenzotriazole (UV-326) and 2-(2 '-hydroxyl-3 ', 5 '-alpha, alpha-dimethylbenzyl) benzo three
One or more in azoles (UV-234)；It is more preferably selected from one or more in UV-327, UV-326 and UV-234.
Described Benzophenones light stabilizer is preferably selected from 2,4-DihydroxyBenzophenone (UV-0), 2-hydroxyl-4-methoxyl group
Benzophenone (UV-9), Octabenzone (UV-531) and methylene (trihydroxybenzophenone) (UV-
1009) one or more in；It is more preferably selected from one or more in UV-9, UV-531 and UV-1009.
Described hindered amine light stabilizer is preferably selected from decanedioic acid two (2,2,6-tetramethyl-4-piperidyl) ester (GW-
480), tricresyl phosphite (1,2,2,6,6 ,-pentamethyl-4-piperidyl) phosphite ester (GW-540), poly-(1-(β-ethyl)-2,2,
6,6-tetramethyl-4-piperidyl) succinic acid ester (GW-622), poly-[6-[(1,1,3,3-tetramethyl butyl)-imino group]-1,
3,5-triazine-2,4-diyl] [2-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino]-hexa-methylene-[4-(2,2,6,6-
Tetramethyl-4-piperidyl)-secondary amino] (GW-944) GW783(weight ratio is GW-944 and GW-622 of 1:1) and poly-{ ［ 6-
(morpholine-4-base)-1,3,5-triazine-2,4-diyl [2-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino ］-six methylenes
Base-［ 4-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino ］ } one or more in (GW-3346)；It is more preferably selected from GW-
622, one or more in GW-944, GW783 and GW-3346.
In the present invention, described light stabilizer and described monomer dianhydride and monomer diamine and mass ratio be preferably
(0.05～5): 100, more preferably (0.05～4): 100, most preferably (0.05～3): 100.
In the present invention, the uv absorption wavelength of different types of light stabilizer is different, light stabilizer and monomer diamine and
The combination of monomer dianhydride has preferred version.In some embodiments of the invention, monomer diamine is 3,4 ＇-diaminodiphenyl ether
With 4,4 ＇-diaminodiphenyl ether, monomer dianhydride is pyromellitic acid dianhydride, and light stabilizer is GW-622；Some realities in the present invention
Executing in example, monomer diamine is 3,4 ＇-diaminodiphenyl ether, and monomer dianhydride is pyromellitic acid dianhydride, and light stabilizer is GW-783；
In some embodiments of the invention, monomer diamine is 4,4 ＇-diaminodiphenyl ether, monomer dianhydride be pyromellitic acid dianhydride and
3,4 ＇-biphenyl dianhydride, light stabilizer is GW-944；In some embodiments of the invention, monomer diamine is 4,4 ＇-diaminourea
Diphenyl ether, monomer dianhydride be pyromellitic acid dianhydride, light stabilizer be GW-944 and UV-327；Other embodiments in the present invention
In, monomer diamine is 4, and 4 ＇-diaminodiphenyl ether, monomer dianhydride are 3,4 ＇-biphenyl dianhydride, light stabilizer be GW-3346 and
UV-1009。
After obtaining polyamic acid spinning solution, polyamic acid spinning solution spinning is obtained polyamic acid fiber.The present invention
Described spinning process is not particularly limited, can be wet spinning, can be dry spinning, it is also possible to for dry spray Wet-spinning
Silk, preferably wet spinning or dry squirt method.
In the present invention, described dry-jet wet spinning preferably includes following steps:
After the filtration of described polyamic acid spinning solution, vacuum defoamation, extruded by spinneret orifice；
Solidify entering coagulating bath by the spinneret orifice extrudate that obtains of extrusion through air layer, then through washing, dried,
Obtain polyamic acid fiber.
First the present invention by after the filtration of polyamic acid spinning solution, vacuum defoamation, is extruded by spinneret orifice.The present invention for
The mode of described filtration and vacuum defoamation is the most unrestricted, mode well known to those skilled in the art.Described the hole diameter of spinneret
It is preferably Φ 0.06～Φ 0.2mm；Described spinneret hole count is preferably 20～1000 holes；Described spray Lapie is preferably 1.5～7.0
Times；Described spray webbing speed preferably 5～100m/min.
Solidify entering coagulating bath by the spinneret orifice extrudate that obtains of extrusion through air layer, then through washing, dried,
Obtain polyamic acid fiber.It is specially after air layer enters coagulating bath molding, then through rinsing bowl, is gathered after drying
Amic acid fiber.Described air layer is highly preferred is 3～100mm, and described coagulating bath is preferably selected from methanol, ethanol, ethylene glycol, fourth
Alcohol, acetone, butanone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide and N-Methyl pyrrolidone
In any one or a few mixed solution with water；Described being dried preferably is dried through hot-rolling or hot gas path, described dry
Environment is preferably air, nitrogen, argon or other noble gas.
In the present invention, described wet spinning preferably includes following steps:
After the filtration of described polyamic acid spinning solution, vacuum defoamation, extruded by spinneret orifice；
Coagulating bath coagulation forming will be entered by the spinneret orifice extrudate that obtain of extrusion, then through washing, dried, obtain
Polyamic acid fiber.
First the present invention by after the filtration of polyamic acid spinning solution, vacuum defoamation, is extruded by spinneret orifice.The present invention for
The mode of described filtration and vacuum defoamation is the most unrestricted, mode well known to those skilled in the art.Described the hole diameter of spinneret
It is preferably Φ 0.04～Φ 0.15mm；Described spinneret hole count is preferably 30～12000 holes；Described spray Lapie be preferably 1.0～
5.0 again；Described spray webbing speed preferably 5～100m/min.
Coagulating bath will be entered by the spinneret orifice extrudate that obtain of extrusion to solidify, then through washing, dried, obtain polyamides
Amino acid fiber.It is specially after entering coagulating bath molding, then through rinsing bowl, obtains polyamic acid fiber after drying.Described solidifying
Gu bath is preferably selected from methanol, ethanol, ethylene glycol, butanol, acetone, butanone, DMF, N, N-dimethylacetamide
Any one or a few mixed solution with water in amine, dimethyl sulfoxide and N-Methyl pyrrolidone；Described being dried is preferably warp
Hot-rolling or hot gas path are dried, and described dry environment is preferably air, nitrogen or noble gas.Described noble gas is preferably
Helium or argon.
In the present invention, described dry spinning preferably includes following steps:
After the filtration of described polyamic acid spinning solution, vacuum defoamation, extruded by spinneret orifice；
The extrudate obtained by spinneret orifice extrusion is passed through the hot gas conduit that distance is longer, after desolvation molding
To polyamic acid fiber.
After obtaining polyamic acid fiber, by polyamic acid fiber imidizate, obtain as-spun polyimide fibers.The present invention
Preferably employ gradient increased temperature heat-treatment furnace to described polyamic acid fiber imidizate.Described imidization environment be preferably air,
The noble gas such as nitrogen, argon；Described imidization temperature is preferably 50 DEG C～500 DEG C, more preferably 50 DEG C～350 DEG C；Described
Programming rate is 1 DEG C/min～30 DEG C/min.The described imidization time is relevant to the temperature of described imidization and programming rate, excellent
Elect 1h～15h as, more preferably 1h～5h.
After imidizate completes, i.e. can get as-spun polyimide fibers.In order to improve the power of described polyimide fiber
Learning performance, the present invention, by as-spun polyimide fibers hot gas spring, obtains polyimide fiber.The drawing temperature of described hot gas spring is excellent
Elect 350 DEG C～550 DEG C as, more preferably 400 DEG C～500 DEG C；The draft ratio of described hot gas spring is preferably 1.0～6.0 times, more
It is preferably 2～5 times；The drawing-off environment of described hot gas spring is air, nitrogen or noble gas.
Compared with prior art, the invention provides the preparation method of a kind of polyimide fiber, comprise the following steps: will
Monomer dianhydride and monomer diamine polymerization, obtain polyamic acid solution；Light stabilizer solution is mixed with polyamic acid solution, obtains
Polyamic acid spinning solution；Polyamic acid spinning solution spinning is obtained polyamic acid fiber；By polyamic acid fiber acid imide
Change, obtain as-spun polyimide fibers；By as-spun polyimide fibers hot gas spring, obtain polyimide fiber；Described monomer two
One or more in formula (I), formula (II) and formula (III) structure of acid anhydride；Described monomer diamine is selected from formula (IV) and formula V knot
One or more in structure.The present invention makes spin by adding certain light stabilizer after monomer diamine and monomer dianhydride are polymerized
Silk solution, after spinning, hot imidization obtains polyimide fiber so that polyimide fiber has good ultra-violet resistance energy；This
Invent and be polymerized by specific monomer diamine and monomer dianhydride, the mechanical property of the polyimide fiber prepared not under
Fall.The technique of the present invention is simple, can be widely applied to spacecraft, loomage, nuclear industry, composite and applied fireproofing
In field.
In order to further illustrate the present invention, below in conjunction with the embodiment preparation side to the polyimide fiber that the present invention provides
Method is described in detail.
Embodiment 1
By 300.360g(1.500mol) 3,4 ＇-diaminodiphenyl ether, 300.360g(1.500mol) 4,4 ＇-diaminourea
Diphenyl ether is dissolved in 9800mL dimethyl sulfoxide, adds 621.642g(2.850mol under stirring) pyromellitic acid dianhydride, 50
DEG C reaction 4 hours, by poly-for 1.222g(［ (1-(β-ethyl)-2,2,6,6-tetramethyl-4-piperidyl) succinic acid ］ ester (GW-622)
It is dissolved in 200mL dimethyl sulfoxide, adds in polyamic acid solution under stirring, continue stirring and within 2 hours, obtain faint yellow viscous
Thick polyamic acid spinning solution.
Dry-jet wet spinning technology path spinning moulding is used after above-mentioned polyamic acid stock solution filtration, vacuum defoamation,
With dosing pump by after the spinning slurry accurate measurement of room temperature, extruding spinneret orifice, wherein, spinneret is 100 holes, aperture Φ
0.15mm, spray Lapie is 1.6 times, and spinning speed is 40m/min；The extrudate obtained will be extruded through air layer by spinneret orifice
Entering volume ratio is in the dimethyl sulfoxide of 1:4 and the coagulating bath of water, is dried to obtain polyamic acid through hot nitrogen path after washing
Fiber, wherein, air layer height is 15mm.
Polyamic acid fiber processes to obtain as-spun polyimide fibers through gradient increased temperature hot imidization stove in a nitrogen environment.Heat
Imidization temperature from 50～400 DEG C, 5 DEG C/min of programming rate.By as-spun polyimide fibers 500 DEG C of drawing-offs in a nitrogen environment
2.8 times obtain polyimide fiber.
The polyimide fiber of the embodiment of the present invention 1 preparation is carried out mechanics performance determining, its fibrous fracture intensity
1.21GPa, modulus 10.75GPa, elongation at break 9.6%.
The polyimide fiber of the embodiment of the present invention 1 preparation is carried out resistance to UV intensity mensuration: be specially above-mentioned preparation
Polyimide fiber measures its intensity after uv light irradiation and keeps data, and irradiation intensity is 10.43w/m2, wave-length coverage is
280～315nm, the results are shown in Table 1, the polyimide fiber ultra-violet resistance that table 1 is the embodiment of the present invention and prepared by comparative example can be surveyed
Determine result.
Embodiment 2
By 630.756g(3.150mol) 3,4 ＇-diaminodiphenyl ether is dissolved in 10000mL N-Methyl pyrrolidone,
196.308g(0.900mol is added under stirring) pyromellitic acid dianhydride and 617.862 g(2.100mol) 4,4 ＇-biphenyl two
Acid anhydride ,-10 DEG C are reacted 10 hours, by the mixture of GW-944 and GW-622 of 14.449g GW-783(mass ratio 1:1) be dissolved in
In 370mL N-Methyl pyrrolidone, add under stirring in polyamic acid solution, continue stirring and obtain faint yellow in 2 hours
The polyamic acid spinning solution of thickness.
After above-mentioned polyamic acid stock solution filtration, vacuum defoamation, use wet spinning technology path spinning moulding, use tricks
Amount pump, by after the spinning slurry accurate measurement of room temperature, is extruded by spinneret orifice, and wherein spinneret is 30 holes, aperture Φ 0.12mm, spray
Lapie is 2.0 times, and spinning speed is 30m/min；The extrudate obtained by spinneret orifice extrusion is entered volume ratio is 1:6's
In the coagulating bath of N-Methyl pyrrolidone and water, after washing, it is dried to obtain polyamic acid fiber through hot nitrogen path.
Polyamic acid fiber processes to obtain as-spun polyimide fibers through gradient increased temperature hot imidization stove under ar gas environment.Heat
Imidization temperature from 50～350 DEG C, 10 DEG C/min of programming rate.By polyimide fiber 350 DEG C of drawing-offs 4.0 under ar gas environment
Obtain polyimide fiber again.
The polyimide fiber of the embodiment of the present invention 2 preparation is carried out mechanics performance determining, its fibrous fracture intensity
1.01GPa, modulus 9.65GPa, elongation at break 10.6%.
The polyimide fiber of the embodiment of the present invention 2 preparation is carried out resistance to UV intensity mensuration: be specially above-mentioned preparation
Polyimide fiber measures its intensity after uv light irradiation and keeps data, and irradiation intensity is 10.43w/m2, wave-length coverage is
280～315nm, the results are shown in Table 1, the polyimide fiber ultra-violet resistance that table 1 is the embodiment of the present invention and prepared by comparative example can be surveyed
Determine result.
Embodiment 3
By 300.360g(1.5mol) 4,4 ＇-diaminodiphenyl ether is dissolved in 2630mL DMF, stirs
Mix under state addition 145.486g(0.667mol) pyromellitic acid dianhydride and 97.975g(0.333mol) 3,4 ＇-biphenyl dianhydride ,-
5 DEG C are reacted 10 hours, by poly-for 1.331g({ [6-[(1,1,3,3-tetramethyl butyl)-imino group]-1,3,5-triazines-2,4-bis-
Base] [2-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl-4-piperidines
Base)-secondary amino]) (GW-944) be dissolved in 50mLN, in dinethylformamide, adds polyamic acid solution under stirring
In, continue stirring and within 2 hours, obtain the polyamic acid stock solution of faint yellow thickness.
Dry-jet wet spinning molding is used after above-mentioned polyamic acid stock solution filtration, vacuum defoamation, will be often with dosing pump
After the spinning slurry accurate measurement of temperature, extruding spinning head, wherein, spinneret is 150 holes, aperture Φ 0.20mm, and speed is
100m/min, spray Lapie is 7.0 times, and spinning speed is 40m/min；The extrudate obtained will be extruded through air by spinneret orifice
Layer enters in the coagulating bath of second alcohol and water that volume ratio is 1:2, is dried to obtain polyamic acid fiber through hot nitrogen path after washing,
Wherein, air layer height is 100mm.
Polyamic acid fiber processes to obtain as-spun polyimide fibers through gradient increased temperature heat-treatment furnace in a nitrogen environment.Heat is sub-
Amination temperature from 50～500 DEG C, 1 DEG C/min of programming rate.By as-spun polyimide fibers 510 DEG C of drawing-offs in a nitrogen environment
2.5 times obtain polyimide fiber.
The polyimide fiber of the embodiment of the present invention 3 preparation is carried out mechanics performance determining, its fibrous fracture intensity
1.4GPa, modulus 20.9GPa, elongation at break 8.32%.
The polyimide fiber of the embodiment of the present invention 3 preparation is carried out resistance to UV intensity mensuration: be specially above-mentioned preparation
Polyimide fiber measures its intensity after uv light irradiation and keeps data, and irradiation intensity is 10.43w/m2, wave-length coverage is
280～315nm, the results are shown in Table 1, the polyimide fiber ultra-violet resistance that table 1 is the embodiment of the present invention and prepared by comparative example can be surveyed
Determine result.
Embodiment 4
By 1601.92g(8.00mol) 4,4 ＇-diaminodiphenyl ether is dissolved in 12000mL N,N-dimethylacetamide,
2181.20g(10.000mol is added under stirring) pyromellitic acid dianhydride, 20 DEG C are reacted 6 hours, by 20.081g GW-944
With 5.021g(2-(2 ＇-hydroxyl-3 ＇, 5 ＇-di-tert-butyl-phenyl)-5-chlorinated benzotriazole) (UV-327) be dissolved in 626mL N,
In N-dimethyl acetylamide, add under stirring in polyamic acid solution, continue stirring and obtain faint yellow thickness in 2 hours
Polyamic acid spinning solution.
Wet spinning molding is used, with dosing pump by room temperature after above-mentioned polyamic acid stock solution filtration, vacuum defoamation
After spinning slurry accurate measurement, extruding spinneret orifice, wherein, spinneret is 12000 holes, aperture Φ 0.04mm, and spray Lapie is 1.0
Times, spinning speed is 20m/min；Through air layer, the extrudate obtained by spinneret orifice extrusion is entered volume ratio is 1:4's
In the coagulating bath of N,N-dimethylacetamide and water, wherein, air layer height is 15mm.
Polyamic acid fiber processes to obtain as-spun polyimide fibers through gradient increased temperature hot imidization stove under air ambient.Heat
Imidization temperature from 50～350 DEG C, 30 DEG C/min of programming rate.By as-spun polyimide fibers under air ambient 450 DEG C lead
Stretch 2.0 times and obtain polyimide fiber.
The polyimide fiber of the embodiment of the present invention 4 preparation is carried out mechanics performance determining, its fibrous fracture intensity
0.60GPa, modulus 5.00GPa, elongation at break 18.2%.
The polyimide fiber of the embodiment of the present invention 4 preparation is carried out resistance to UV intensity mensuration: be specially above-mentioned preparation
Polyimide fiber measures its intensity after uv light irradiation and keeps data, and irradiation intensity is 10.43w/m2, wave-length coverage is
280～315nm, the results are shown in Table 1, the polyimide fiber ultra-violet resistance that table 1 is the embodiment of the present invention and prepared by comparative example can be surveyed
Determine result.
Embodiment 5
By 200.24g(1.000mol) 4,4 ＇-diaminodiphenyl ether is dissolved in 2900mL N,N-dimethylacetamide,
294.22g(1.000mol is added under stirring) 3,4 ＇-biphenyl dianhydride ,-5 DEG C of reactions obtain faint yellow thickness in 10 hours
Polyamic acid solution, by poly-for 0.198g({ ［ 6-(morpholine-4-base)-1,3,5-triazines-2,4-diyl ］ ［ 2-(2,2,6,6-tetramethyls
Base-4-piperidyl)-secondary amino ］-hexa-methylene-4-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino ］) (GW-3346)
It is dissolved in 76mL DMAC N,N' dimethyl acetamide with the mixture (UV-1009) of 0.049g methylene (trihydroxybenzophenone),
Add under stirring in polyamic acid solution, continue stirring and obtain spinning solution in 2 hours.
Dry-jet wet spinning molding is used after above-mentioned polyamic acid stock solution filtration, vacuum defoamation, will be often with dosing pump
After the spinning slurry accurate measurement of temperature, extruding spinneret orifice, wherein, spinneret is 1000 holes, aperture Φ 0.06mm, spinning speed
For 5m/min, spray Lapie is 3.0 times；Through air layer, the extrudate obtained by spinneret orifice extrusion is entered volume ratio is 1:3
DMF and water coagulating bath in, be dried to obtain polyamic acid fiber through hot nitrogen path after washing, its
In, air layer height is 30mm.
Polyamic acid fiber processes to obtain as-spun polyimide fibers through gradient increased temperature hot imidization stove in a nitrogen environment.Heat
Imidization temperature from 50～500 DEG C, 1 DEG C/min of programming rate.The as-spun polyimide fibers obtained 550 DEG C in a nitrogen environment
Drawing-off 2.5 times obtains polyimide fiber.
The polyimide fiber of the embodiment of the present invention 5 preparation is carried out mechanics performance determining, its fibrous fracture intensity
0.97GPa, modulus 11.36GPa, elongation at break 8.3%.
The polyimide fiber of the embodiment of the present invention 5 preparation is carried out resistance to UV intensity mensuration: be specially above-mentioned preparation
Polyimide fiber measures its intensity after uv light irradiation and keeps data, and irradiation intensity is 10.43w/m2, wave-length coverage is
280～315nm, the results are shown in Table 1, the polyimide fiber ultra-violet resistance that table 1 is the embodiment of the present invention and prepared by comparative example can be surveyed
Determine result.
Comparative example 1
By 300.360g(1.500mol) 4,4 ＇-diaminodiphenyl ether is dissolved in 2630ml DMF,
145.486g(0.667mol is added under stirring) pyromellitic acid dianhydride and 97.975g(0.333mol) 3,4 '-biphenyl two
Acid anhydride ,-5 DEG C of reactions obtain the polyamic acid stock solution of faint yellow thickness for 10 hours.
Dry-jet wet spinning molding is used after above-mentioned polyamic acid stock solution filtration, vacuum defoamation, will be often with dosing pump
After the spinning slurry accurate measurement of temperature, extruding spinning head, wherein spinneret is 150 holes, aperture Φ 0.20mm, and speed is
100m/min, spray Lapie is 7.0 times, and spinning speed is 40m/min；The extrudate obtained will be extruded through air by spinneret orifice
Layer enters in the coagulating bath of second alcohol and water (1:2 volume ratio), is dried to obtain polyamic acid fiber through hot-rolling after washing, wherein, empty
Gas-bearing formation height is 100mm.
Polyamic acid fiber processes to obtain polyimide fiber through gradient increased temperature heat-treatment furnace in a nitrogen environment.Hot imidization
Temperature from 50～500 DEG C, 1 DEG C/min of programming rate.The polyimide fiber obtained 510 DEG C of drawing-offs 2.5 times in a nitrogen environment
Obtain polyimides finished fiber.
The polyimide fiber of comparative example 1 of the present invention preparation is carried out mechanics performance determining, its fibrous fracture intensity
1.38GPa, modulus 20.0GPa, elongation at break 8.3%.
The polyimide fiber of comparative example 1 of the present invention preparation is carried out resistance to UV intensity mensuration: be specially above-mentioned preparation
Polyimide fiber measures its intensity after uv light irradiation and keeps data, and irradiation intensity is 10.43w/m2, wave-length coverage is
280～315nm, the results are shown in Table 1, the polyimide fiber ultra-violet resistance that table 1 is the embodiment of the present invention and prepared by comparative example can be surveyed
Determine result.
Comparative example 2
Polyimides finished fiber is prepared according to method disclosed in CN101338462A embodiment 2.
The polyimide fiber of above-mentioned preparation is carried out mechanics performance determining, its fibrous fracture intensity 1.30GPa, modulus
20.6GPa, elongation at break 8.3%.
The polyimide fiber of comparative example 2 of the present invention preparation is carried out resistance to UV intensity mensuration: be specially above-mentioned preparation
Polyimide fiber measures its intensity after uv light irradiation and keeps data, and irradiation intensity is 10.43w/m2, wave-length coverage is
280～315nm, the results are shown in Table 1, the polyimide fiber ultra-violet resistance that table 1 is the embodiment of the present invention and prepared by comparative example can be surveyed
Determine result.
The polyimide fiber ultra-violet resistance energy measurement result that table 1 is the embodiment of the present invention and prepared by comparative example.
As shown in Table 1, the polyimide fiber that the embodiment of the present invention prepares has good ultra-violet resistance energy.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. the preparation method of a polyimide fiber, it is characterised in that comprise the following steps:
Monomer dianhydride and monomer diamine are polymerized, obtain polyamic acid solution；
Light stabilizer solution is mixed with polyamic acid solution, obtains polyamic acid spinning solution；
Polyamic acid spinning solution spinning is obtained polyamic acid fiber；
By polyamic acid fiber imidizate, obtain as-spun polyimide fibers；
By as-spun polyimide fibers hot gas spring, obtain polyimide fiber；
Described monomer diamine is 3,4 ＇-diaminodiphenyl ether and 4,4 ＇-diaminodiphenyl ether, and monomer dianhydride is PMA two
Acid anhydride, light stabilizer is poly-[(1-(β-ethyl)-2,2,6,6-tetramethyl-4-piperidyl) succinic acid] ester；
Or described monomer diamine is 3,4 ＇-diaminodiphenyl ether, monomer dianhydride is pyromellitic acid dianhydride, and light stabilizer is attached most importance to
Amount than be 1:1 poly-[6-[(1,1,3,3-tetramethyl butyl)-imino group]-1,3,5-triazine-2,4-diyl] [2-(2,2,
6,6-tetramethyl-4-piperidyl)-secondary amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino] } and
Poly-[(1-(β-ethyl)-2,2,6,6-tetramethyl-4-piperidyl) succinic acid] ester；
Or described monomer diamine is 4,4 ＇-diaminodiphenyl ether, monomer dianhydride is pyromellitic acid dianhydride and 3,4 ＇-biphenyl two
Acid anhydride, light stabilizer be poly-[6-[(1,1,3,3-tetramethyl butyl)-imino group]-1,3,5-triazines-2,4-diyl] [2-(2,
2,6,6-tetramethyl-4-piperidyl)-secondary amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl-4-piperidyl)-secondary ammonia
Base] }；
Or described monomer diamine be 4,4 ＇-diaminodiphenyl ether, monomer dianhydride be pyromellitic acid dianhydride, light stabilizer be poly-
{ [6-[(1,1,3,3-tetramethyl butyl)-imino group]-1,3,5-triazine-2,4-diyl] [2-(2,2,6,6-tetramethyl-4-piperazine
Piperidinyl)-secondary amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino] } and 2-(2 '-hydroxyl-3 ',
5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole；
Or described monomer diamine be 4,4 ＇-diaminodiphenyl ether, monomer dianhydride be that 3,4 ＇-biphenyl dianhydride, light stabilizer are
Poly-{ [6-(morpholine-4-base)-1,3,5-triazine-2,4-diyl [2-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino]-six
Methylene-[4-(2,2,6,6-tetramethyl-4-piperidyl)-secondary amino] } and methylene (trihydroxybenzophenone).
Preparation method the most according to claim 1, it is characterised in that in described light stabilizer solution, solvent is selected from N, N-
One or more in dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and N-Methyl pyrrolidone.
Preparation method the most according to claim 1, it is characterised in that described light stabilizer and described monomer dianhydride and monomer
The mass ratio of the sum of diamidogen is (0.05～5): 100.
Preparation method the most according to claim 1, it is characterised in that the mol ratio of described monomer dianhydride and monomer diamine is
1:0.8～1.5.
Preparation method the most according to claim 1, it is characterised in that the quality of polyamic acid in described polyamic acid solution
Concentration is 5～35wt%.
Preparation method the most according to claim 1, it is characterised in that described polymerization temperature is-10 DEG C～50 DEG C.
Preparation method the most according to claim 1, it is characterised in that described polyamic acid spinning solution is carried out spinning tool
Body comprises the following steps:
After the filtration of described polyamic acid spinning solution, vacuum defoamation, extruded by spinneret orifice；
Solidify entering coagulating bath by the spinneret orifice extrudate that obtains of extrusion through air layer, then through washing, dried, obtain
Polyamic acid fiber.
Preparation method the most according to claim 1, it is characterised in that the temperature of described imidizate is 50 DEG C～500 DEG C；
The programming rate of described imidizate is 1 DEG C/min～30 DEG C/min.
Preparation method the most according to claim 1, it is characterised in that the drawing temperature of described hot gas spring is 350 DEG C～550
DEG C, the draft ratio of described hot gas spring is 1～6 times.
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| CN110863258B (en) * | 2019-11-26 | 2021-04-27 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN112695402B (en) * | 2020-12-24 | 2022-12-20 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN116103779B (en) * | 2023-02-14 | 2024-04-12 | 江苏奥神新材料股份有限公司 | Polyimide fiber with high heat resistance and preparation method thereof |
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| CN101338462B (en) * | 2008-08-20 | 2010-09-29 | 中国科学院长春应用化学研究所 | Method for preparing polyimide fiber |
| CN102432597A (en) * | 2011-09-13 | 2012-05-02 | 大连化工研究设计院 | Benzotriazole light stabilizer containing hindered amine genes |
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