CN107385878A - Utilize supercritical CO2The method that fluid technique carries out the inorganization modification of aramid fiber - Google Patents
Utilize supercritical CO2The method that fluid technique carries out the inorganization modification of aramid fiber Download PDFInfo
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- CN107385878A CN107385878A CN201710630413.1A CN201710630413A CN107385878A CN 107385878 A CN107385878 A CN 107385878A CN 201710630413 A CN201710630413 A CN 201710630413A CN 107385878 A CN107385878 A CN 107385878A
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- aramid fiber
- light stabilizer
- presoma
- fibers
- inorganic light
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000012986 modification Methods 0.000 title claims abstract description 22
- 230000004048 modification Effects 0.000 title claims abstract description 22
- 239000012530 fluid Substances 0.000 title claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 135
- 239000004611 light stabiliser Substances 0.000 claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 230000008961 swelling Effects 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 4
- 229920000784 Nomex Polymers 0.000 claims description 24
- 239000004763 nomex Substances 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004760 aramid Substances 0.000 claims description 14
- 229920003235 aromatic polyamide Polymers 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000271 Kevlar® Polymers 0.000 claims description 3
- 239000004761 kevlar Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001494 Technora Polymers 0.000 claims description 2
- 229920000561 Twaron Polymers 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004950 technora Substances 0.000 claims description 2
- 239000004762 twaron Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 23
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008595 infiltration Effects 0.000 abstract description 3
- 238000001764 infiltration Methods 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- 238000001035 drying Methods 0.000 description 14
- 229920003369 Kevlar® 49 Polymers 0.000 description 13
- 229920003368 Kevlar® 29 Polymers 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 230000032683 aging Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DIWNCNINVWYUCD-UHFFFAOYSA-N acetyl acetate;zinc Chemical compound [Zn].CC(=O)OC(C)=O DIWNCNINVWYUCD-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- GONSYFXEPMZGNN-UHFFFAOYSA-N acetic acid;propan-1-ol Chemical compound CCCO.CC(O)=O GONSYFXEPMZGNN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- -1 specifically Polymers 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
It the present invention relates to the use of supercritical CO2The method that fluid technique carries out the inorganization modification of aramid fiber, including：Step 1), aramid fiber and the supercritical CO dissolved with inorganic light stabilizer presoma2Fluid carries out swelling reaction, obtains the aramid fiber containing inorganic light stabilizer presoma；Step 2), the aramid fiber containing inorganic light stabilizer presoma is placed in the alcoholic solvent containing alkali solute or acid solute, thermally decomposes to generate the modification of aramid fiber containing inorganic light stabilizer.The present invention utilizes supercritical CO2The strong infiltration of fluid, carry effect, carry small molecule light stabilizer presoma and enter the surface of aramid fiber and internal amorphous region, on the one hand the mechanical property of fiber is improved using the plastication of supercritical carbon dioxide, on the other hand can be controlled in the structure of the nanometer light stabilizer of amorphous region, do not reunite, improve the anti-light degradation capability of fiber.
Description
Technical field
The invention belongs to fibre modification field, more particularly to utilizing supercritical CO2Fluid technique carry out aramid fiber without
The method that machineization is modified.
Background technology
Aramid fiber refers to the high-performance fiber containing aromatic series rigid chain of the phenyl ring more than 85%, have high intensity, high-modulus,
The premium properties such as high temperature resistant, chemically-resistant solvent, proportion is small, are widely used in advanced strategic arms, e.g., airspace engine, soldier
The fields such as shellproof protector, Aero-Space, automobile, optical fiber enhancing, hawser, are important strategic materials.
It is made up of inside aramid fiber height-oriented crystal region and amorphous region, amorphous region part is by fento and micro-
Hole forms, and the fracture of fiber typically first occurs in amorphous region.Contain substantial amounts of C-N keys and double bond in aramid fiber strand, for
Wavelength is that 300~450nm ultraviolet light and some visible light are easier to absorb, for a long time under aerobic environment and ultraviolet light
Light aging degraded can occur, the defects of fiber becomes fragile discoloration, and surface cracks, under causing aramid fiber products machinery performance gradual
Drop, influences the life-span of fiber, restricts its application.The anti-light degradation property of aramid fiber is poor, influences its outdoor, aerospace applications
The life-span of product, it is often more important that influence the safe to use of the product such as shellproof, be to capture unsolved difficult scientific problems for a long time.
Existing research is taken aramid fiber surface modification cover the methods of to protect fiber, make its not by ultraviolet light with can
See the destruction of light, specifically, the material containing UV light stabilizing agent or the protective layer containing light stabilizer coated in fiber sheath,
Such as SiO2、TiO2, ZnO etc., but due to fiber surface smoother, the functional group that can be reacted is few, and anti-light degraded protective layer can only
It is adhered to fiber surface, and poor adhesion.The anti-light degradation material of surface coating can not stop the intrusion of ultraviolet completely, and
Because containing largely photodegradative end moieties easily occur for amorphous region inside aramid fiber, make its to weaker ultraviolet light still
Compare sensitive, light degradation easily occurs, especially after anti-light degradation material comes off, the amorphous of aramid fiber is more easy to that light occurs
Degraded aging.
Therefore, how light stabilizer is introduced to the amorphous region of fibrous inside, especially fibrous inside, overcomes fiber surface
The surface that modified covering is brought covers the problems such as stability is poor, anti-light solution ability is weak, method of modifying application limitation is big, improves fiber
Low-fiber mechanical property is not dropped again while anti-light degradation capability, is still the technical problem for needing further to solve.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides and utilizes supercritical CO2It is inorganization that fluid technique carries out aramid fiber
Modified method.
The technical scheme is that：Utilize supercritical CO2The method that fluid technique carries out the inorganization modification of aramid fiber,
Comprise the following steps：
Step 1), aramid fiber is with dissolving the inorganic supercritical CO for having light stabilizer presoma2Fluid carries out swelling reaction,
Obtain the aramid fiber containing inorganic light stabilizer presoma；
Step 2), the aramid fiber containing inorganic light stabilizer presoma is placed in alkaline alcohol solution or acidity alcohol solution
In, thermally decompose to generate the modification of aramid fiber containing inorganic light stabilizer.
In step 1), first aramid fiber and inorganic light stabilizer presoma are placed in reaction vessel, aramid fiber and nothing
Machine light stabilizer presoma does not contact；Carbon dioxide is passed through to generating supercritical carbon dioxide fluid to reaction vessel again；
Supercritical carbon dioxide fluid carries the inorganic light stabilizer presoma of dissolving, carries out swelling reaction with aramid fiber, is contained
There is the aramid fiber of inorganic light stabilizer presoma.Swelling reaction refers to the light stabilizer of supercritical carbon dioxide carrying with solvent
The mode of infiltration contacts with aramid fiber.
In step 1), reaction vessel is passed through before carbon dioxide, first carries out exhaust outlet processing.Specifically, it is vented
The processing mode of draining is that first reaction vessel is heated, is vapor to water transform；Reaction vessel is carried out afterwards to vacuumize place
Reason.The purpose of exhaust outlet processing is air and moisture in exclusion closed container, eliminates oxygen isoreactivity gas in air
With influence of the moisture to experiment.
In step 1), aramid fiber be p-aramid fiber Kevlar, Nomex fiber, Twaron fibers, Technora fibers,
Fragrant III fibers or F-12 fibers, inorganic light stabilizer presoma are nano-TiO 2 precursor or nanometer zinc oxide precursor,
The addition of inorganic light stabilizer presoma is the 1~10% of the carbon dioxide quality being passed through, it is preferable that before inorganic light stabilizer
The addition for driving body is the 2.5~5% of the carbon dioxide quality being passed through；The addition of inorganic light stabilizer presoma is that aramid fiber is fine
Tie up the 15%~60% of quality, it is preferable that the addition of inorganic light stabilizer presoma is the 20~50% of aramid fiber quality.
In step 1), the formation condition of supercritical carbon dioxide fluid is 50~160 DEG C of temperature, 7~28Mpa of pressure.Cause
Temperature is CO2An important indicator in Supercritical Conditions, only temperature are more than 31 DEG C, coordinate certain pressure real
Existing CO2Supercritical Conditions, and pressure and temperature effect CO2Concentration in autoclave, and then influence light stabilizer
The concentration of presoma.Preferably, the formation condition of supercritical carbon dioxide fluid is 50~100 DEG C of temperature, pressure 10~
15Mpa。
Reaction vessel is heated by electrical heating or oil bath heating mode.
In step 1), the time for being swelled reaction is 20~120min.Preferably, the time for being swelled reaction is 30~90min.
In step 1), after swelling reaction terminates, reaction vessel release.Specifically, the release time is 1~10min, preferably
Ground, release time are 1~5min.
Nano-TiO 2 precursor is titanium tetrachloride, tetrabutyl titanate or iso-butyl titanate, nanometer zinc oxide precursor
For hydration zinc acetate, zinc nitrate or zinc chloride.
In aramid fiber containing inorganic light stabilizer presoma, inorganic light stabilizer presoma accounts for aramid fiber quality
1%~10%.Preferably, inorganic light stabilizer presoma accounts for the 1.5%~7% of aramid fiber quality.
In step 1), the cleaned drying process of aramid fiber, specifically, aramid fiber is placed in organic solvent, and constant temperature surpasses
After sound washing, vacuum drying.Organic solvent is acetone, 60~95 DEG C of ultrasonic temperature, 1~2h of ultrasonic time；Drying temperature 70~
100 DEG C, 1~8h of drying time.Preferably, 75~85 DEG C of ultrasonic temperature, 1~1.2h of ultrasonic time；75~85 DEG C of drying temperature,
1~2h of drying time.
In step 2), when inorganic light stabilizer presoma is nanometer zinc oxide precursor, alcoholic solution is alkaline alcohol solution.
In step 2), alkaline alcohol solution pH=7~10, alkali solute is hydrazine hydrate, ammoniacal liquor, NaOH, KOH, it is preferable that alkali
Property alcoholic solution pH=8~9, alkali solute KOH；The concentration of acid solute is 0.2~1mol/L in acidity alcohol solution, acid molten
Matter is hydrochloric acid or acetic acid, it is preferable that the concentration of acid solute is 0.25~0.9mol/L in acidity alcohol solution, and acid solute is
Acetic acid.
In step 2), thermally decompose and thermally decomposed for backflow, 80~120 DEG C of 1~3h of backflow thermal decomposition.Preferably, 85~100 DEG C
1.5~2.5h of backflow thermal decomposition.
In step 2), the cleaned drying process of modification of aramid fiber, specifically, modification of aramid fiber is placed in organic solvent
In, after constant temp to constant weight, vacuum drying.Organic solvent is acetone, ethanol or methanol, 60~95 DEG C of wash temperature, is dried
70~120 DEG C of temperature, 1~2h of drying time.Preferably, organic solvent is acetone, 75~85 DEG C of wash temperature, drying temperature 75
~100 DEG C, 1~1.2h of drying time.
Compared with prior art, the invention has the advantages that：
1st, aramid fiber causes in general chemical combination because of the rigid molecule chain structure with higher crystallinity and arranged regular
Thing is difficult to penetrate into fibrous inside, and supercritical CO2The strong infiltration of fluid, effect is carried, micromolecular compound can be carried and entered
Enter inside aramid fiber, especially into the amorphous region of fibrous inside.
2nd, the present invention utilizes supercritical CO2Light stabilizer presoma small molecule is brought into the table of aramid fiber by fluid technique
Face and internal amorphous region, the light stabilizer presoma for introducing fiber surface and internal amorphous region act on conversion through thermal decomposition
For light stabilizer, because aramid fiber amorphous region is in nano-micrometre yardstick, therefore, it is steady nanometer light can be formed in amorphous region
Determine agent, and this nanometer of light stabilizer structure-controllable, do not reunite, improve the anti-light degradation capability of fiber.At the same time, aramid fiber
The nanometer light stabilizer that fiber amorphous region is formed, further improve the mechanical property of aramid fiber.And nanometer light stabilizer with
Amorphous region strong bonded, does not fall off separation, and anti-light degradation capability and mechanical property keep permanently effective.
3rd, after the ultraviolet light burin-in process of 7 days, relative to unmodified aramid fiber, the intensity of modification of aramid fiber
Conservation rate improves 9.3~26.7%, and the modulus conservation rate of aramid fiber improves 4.4~19.6%, modification of aramid fiber it is anti-light
Degradation capability significantly improves.
4th, 2.24~11.54% are improved relative to unmodified aramid fiber, the tensile strength of modification of aramid fiber, modulus carries
It is high by 0.6~5.15%, that is to say, that modification of aramid fiber improves the power of itself again while anti-light degradation capability is improved
Learn performance.
5th, the present invention utilizes supercritical CO2The method that fluid technique carries out inorganization modification to aramid fiber, there is economy
Environmental protection, react controllable, solvent and separated with product simply, it is little to the Effect on Mechanical Properties of fiber the advantages that, larger industry be present
Application value.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
(1) 5g Kevlar49 fibers are put into acetone solvent, 80 DEG C of supersound washing 1h, taken out, 80 DEG C of vacuum drying
2h。
(2) the Kevlar49 fibers of step (1) scrubbed drying process and 2g tetrabutyl titanates are placed in 2L reaction under high pressures
In kettle, Kevlar49 fibers are placed in metal frame, it is not contacted with tetrabutyl titanate.
(3) mode of oil bath heating is utilized, 2L autoclaves are heated to 100 DEG C, first vacuumizes and excludes air in kettle
And water, after temperature in the kettle drops to 80 DEG C, CO is filled with into kettle2, pressure in kettle is reached 10Mpa, in supercritical CO2State, titanium
The quality of sour N-butyl is 3% of carbon dioxide quality in reactor；After swelling reaction 40min, reacting kettle inner pressure 3min is unloaded
To normal pressure, the Kevlar49 fibers containing 0.17g tetrabutyl titanates are obtained.
(4) the Kevlar49 fibers containing 0.17g tetrabutyl titanates are placed in 50mL ethanol acetate solution, the concentration of acetic acid
For 0.29mol/L, 85 DEG C of backflow 2h, Modified K evlar49 fibers are obtained.
(5) Modified K evlar49 fibers acetone is after 80 DEG C of cleaning 1h to constant weight, 80 DEG C of vacuum drying 1h..
(6) strength of filament instrument tested K evlar49 fibers, Modified K evlar49 fibers, the Kevlar49 of burin-in process are utilized
The mechanical property of fiber and the Modified K evlar49 fibers of burin-in process, ageing method are：By Kevlar49 fibers and change
Property Kevlar49 fibers be placed under accelerating ultraviolet illumination and carry out degradation in 7 days.
The monofilament tensile strength of Kevlar49 fibers is 22.3CN/dtex, modulus 780.4CN/dtex；Burin-in process
The tensile strength of Kevlar49 fibers is 10CN/dtex, strength retention 45.4%, modulus 460.5CN/dtex, and modulus is protected
Holdup is 58.9%.
The tensile strength of Modified K evlar49 fibers is 22.8CN/dtex, modulus 790.6CN/dtex；Burin-in process
The tensile strength of Modified K evlar49 fibers is 16.5CN/dtex, strength retention 72.1%, modulus 620.4CN/
Dtex, modulus conservation rate are 78.5%.Compared with the Kevlar49 fibers of non-modified processing, its mechanical property improves, anti-light
Degradation capability improves.
Compared with the Kevlar49 fibers of non-modified processing, through senile experiment, the stretching of Modified K evlar49 fibers is strong
Spend conservation rate and improve 26.7%, modulus conservation rate improves 19.6%, and anti-light degradation capability improves.
Compared with unmodified Kevlar49 fibers, the tensile strength of Modified K evlar49 fibers improves 2.24%, modulus
1.3% is improved, mechanical property also improves simultaneously.
Embodiment 2
(1) 5.5g Kevlar29 fibers are put into acetone solvent, 80 DEG C of supersound washing 1h, taken out, 80 DEG C of vacuum drying
2h。
(2) the Kevlar29 fibers of step (1) scrubbed drying process and 2.5g titanium tetrachlorides are placed in 2L reaction under high pressures
In kettle, Kevlar29 fibers are placed in metal frame, it is not contacted with titanium tetrachloride.
(3) mode of oil bath heating is utilized, 2L autoclaves are heated to 100 DEG C, first vacuumizes and excludes air in kettle
And water, after temperature in the kettle drops to 80 DEG C, CO is filled with into kettle2, pressure in kettle is reached 10Mpa, in supercritical CO2State, four
The quality of titanium chloride is 2.5% of carbon dioxide quality in reactor；After swelling reaction 40min, reacting kettle inner pressure 5min is unloaded
To normal pressure, the Kevlar29 fibers containing 0.1g titanium tetrachlorides are obtained.
(4) the Kevlar29 fibers containing 0.1g titanium tetrachlorides are placed in 50mL acetic acid propanol solutions, and the concentration of acetic acid is
0.86mol/L, 95 DEG C of backflow 1.5h, obtains Modified K evlar29 fibers.
(5) Modified K evlar29 fibers acetone is after 80 DEG C of cleaning 1h to constant weight, 80 DEG C of vacuum drying 1h..
(6) strength of filament instrument tested K evlar29 fibers, Modified K evlar29 fibers, the Kevlar29 of burin-in process are utilized
The mechanical property of fiber and the Modified K evlar29 fibers of burin-in process, ageing method are：By Kevlar29 fibers and change
Property Kevlar29 fibers be placed under accelerating ultraviolet illumination and carry out degradation in 7 days.
The monofilament tensile strength of Kevlar29 fibers is 20.1CN/dtex, modulus 480.2CN/dtex；Burin-in process
The tensile strength of Kevlar fibers is 11.5CN/dtex, strength retention 57.2%, modulus 338.5CN/dtex, and modulus is protected
Holdup is 70.5%.
The tensile strength of Modified K evlar29 fibers is 20.9CN/dtex, modulus 490.6CN/dtex；Burin-in process
The tensile strength of Modified K evlar29 fibers is 17.5CN/dtex, strength retention 83.7%, modulus 430.2CN/
Dtex, modulus conservation rate are 87.8%.Compared with the Kevlar29 fibers of non-modified processing, its mechanical property improves, anti-light
Degradation capability improves.
Compared with the Kevlar29 fibers of non-modified processing, after senile experiment, the stretching of Modified K evlar29 fibers
Strength retention improves 26.5%, and modulus conservation rate improves 17.3%, and anti-light degradation capability improves.
Compared with unmodified Kevlar29 fibers, the tensile strength of Modified K evlar29 fibers improves 3.98%, modulus
2.16% is improved, mechanical property also improves simultaneously.
Embodiment 3
(1) 6g Tecnora fibers are put into acetone solvent, 80 DEG C of supersound washing 1h, taken out, 80 DEG C of vacuum drying 2h.
(2) the Tecnora fibers of step (1) scrubbed drying process and 1.2g titanium tetrachlorides are placed in 2L autoclaves
Interior, Tecnora fibers are placed in metal frame, it is not contacted with titanium tetrachloride.
(3) mode of oil bath heating is utilized, 2L autoclaves are heated to 100 DEG C, first vacuumizes and excludes air in kettle
And water, after temperature in the kettle drops to 70 DEG C, CO is filled with into kettle2, pressure in kettle is reached 13Mpa, in supercritical CO2State, four
The quality of titanium chloride is 3.5% of carbon dioxide quality in reactor；After swelling reaction 60min, reacting kettle inner pressure 3min is unloaded
To normal pressure, the Tecnora fibers containing 0.2g titanium tetrachlorides are obtained.
(4) the Tecnora fibers containing 0.2g titanium tetrachlorides are placed in the 50mL potassium hydroxide-ethanol solutions that pH is 8~9,
90 DEG C of backflow 2h, obtain being modified Tecnora fibers.
(5) modified Tecnora fibers acetone is after 80 DEG C of cleaning 1h to constant weight, 80 DEG C of vacuum drying 1h..
(6) Tecnora using strength of filament instrument test Tecnora fibers, modified Tecnora fibers, burin-in process is fine
The mechanical property of the modification Tecnora fibers of peacekeeping burin-in process, ageing method are：By Tecnora fibers and modification
Tecnora fibers are placed on illumination under accelerating ultraviolet and carry out degradation in 7 days.
The monofilament tensile strength of Tecnora fibers is 20.2CN/dtex, modulus 520.4CN/dtex；Burin-in process
The tensile strength of Tecnora fibers is 9.2CN/dtex, strength retention 45.4%, modulus 410.5CN/dtex, and modulus is protected
Holdup is 78.9%.
The tensile strength of modified Tecnora fibers is 20.8CN/dtex, modulus 540.6CN/dtex；Burin-in process
The tensile strength of modified Tecnora fibers is 8.5CN/dtex, strength retention 40.9%, modulus 450.4CN/dtex,
Modulus conservation rate is 83.3%.Compared with the Tecnora fibers of non-modified processing, its mechanical property improves, anti-light degraded energy
Power improves.
Compared with the Tecnora fibers of non-modified processing, after senile experiment, the modulus of modified Tecnora fibers is protected
Holdup improves 4.4%, and anti-light degradation capability improves.
Compared with unmodified Tecnora fibers, the tensile strength of modified Tecnora fibers improves 2.97%, and modulus carries
High by 3.88%, mechanical property also improves simultaneously.
Embodiment 4
(1) 4.8g Nomex fibers are put into acetone solvent, 80 DEG C of supersound washing 1h, taken out, 80 DEG C of vacuum drying 2h.
(2) the Nomex fibers of step (1) scrubbed drying process and 1.2g acetic anhydride zinc are placed in 2L autoclaves
Interior, Nomex fibers are placed in metal frame, it is not contacted with acetic anhydride zinc.
(3) mode of oil bath heating is utilized, 2L autoclaves are heated to 100 DEG C, first vacuumizes and excludes air in kettle
And water, CO is filled with into kettle2, pressure in kettle is reached 13Mpa, in supercritical CO2State, the quality of acetic anhydride zinc is anti-
Answer 3% of carbon dioxide quality in kettle；After swelling reaction 90min, reacting kettle inner pressure 4min is unloaded to normal pressure, is obtained containing 0.3g
The Nomex fibers of acetic anhydride zinc.
(4) the Nomex fibers containing 0.3g acetic anhydride zinc are placed in the 60mL potassium hydroxide-ethanol solutions that pH is 8~9,
90 DEG C of backflow 2h, obtain being modified Nomex fibers.
(5) modified Nomex fibers acetone is after 80 DEG C of cleaning 1h to constant weight, 80 DEG C of vacuum drying 1h..
(6) strength of filament instrument test Nomex fibers, modified Nomex fibers, the Nomex fibers of burin-in process and old are utilized
Change the mechanical property of the modification Nomex fibers of processing, ageing method is：Nomex fibers and modified Nomex fibers are placed on
Illumination carries out degradation in 7 days under accelerating ultraviolet.
The monofilament tensile strength of Nomex fibers is 5.2CN/dtex, modulus 120.4CN/dtex；Burin-in process
The tensile strength of Nomex fibers is 3.2CN/dtex, strength retention 61.5%, modulus 80.5CN/dtex, modulus conservation rate
For 66.8%.
The tensile strength of modified Nomex fibers is 5.8CN/dtex, modulus 126.6CN/dtex；The modification of burin-in process
The tensile strength of Nomex fibers is 4.8CN/dtex, strength retention 82.7%, modulus 100.6CN/dtex, and modulus is protected
Holdup is 83.6%.Compared with the Nomex fibers of non-modified processing, its mechanical property improves, and anti-light degradation capability improves.
Compared with the Nomex fibers of non-modified processing, after senile experiment, the tensile strength of modified Nomex fibers is protected
Holdup improves 21.2%, and modulus conservation rate improves 16.8%, and anti-light degradation capability improves.
Compared with unmodified Nomex fibers, the tensile strength of modified Nomex fibers improves 11.54%, and modulus improves
5.15%, mechanical property also improves simultaneously.
Embodiment 5
(1) 6g aramid III fibers are put into acetone solvent, 80 DEG C of supersound washing 1h, taken out, 80 DEG C of vacuum drying 2h.
(2) aramid III fiber of step (1) scrubbed drying process and 1.2g anhydrous zinc chlorides are placed in 2L reaction under high pressures
In kettle, aramid III fiber is placed in metal frame, it is not contacted with anhydrous zinc chloride.
(3) mode of oil bath heating is utilized, 2L autoclaves are heated to 100 DEG C, first vacuumizes and excludes air in kettle
And water, then CO is filled with into kettle2, pressure in kettle is reached 13Mpa, in supercritical CO2State, the quality of anhydrous zinc chloride are
The 5% of carbon dioxide quality in reactor；After swelling reaction 90min, reacting kettle inner pressure 5min is unloaded to normal pressure, is contained
The aramid III fiber of 0.3g anhydrous zinc chlorides.
(4) aramid III fiber containing 0.3g anhydrous zinc chlorides is placed in the 60mL potassium hydroxide-ethanol solutions that PH is 8~9
In, 90 DEG C of backflow 2h, obtain modifying aramid fiber III fibers.
(5) modifying aramid fiber III fibers acetone is after 80 DEG C of cleaning 1h to constant weight, 80 DEG C of vacuum drying 1h..
(6) aramid III using strength of filament instrument test aramid III fiber, modifying aramid fiber III fibers, burin-in process is fine
The mechanical property of the modifying aramid fiber III fibers of peacekeeping burin-in process, ageing method are：By aramid III fiber and modified virtue
Synthetic fibre III fibers are placed on illumination under accelerating ultraviolet and carry out degradation in 7 days.
The monofilament tensile strength of aramid III fiber is 29.2CN/dtex, modulus 1020.4CN/dtex；Burin-in process
The tensile strength of aramid III fiber is 23.2CN/dtex, strength retention 79.4%, modulus 680.5CN/dtex, and modulus is protected
Holdup is 66.9%.
The tensile strength of modifying aramid fiber III fibers is 30.2CN/dtex, modulus 1026.6CN/dtex；Burin-in process
The tensile strength of modifying aramid fiber III fibers is 26.8CN/dtex, strength retention 88.7%, modulus 883.4CN/dtex,
Modulus conservation rate is 86.5%.Compared with the aramid III fiber of non-modified processing, its mechanical property improves, anti-light degraded energy
Power improves.
Compared with the aramid III fiber of non-modified processing, after senile experiment, the stretching of modifying aramid fiber III fibers is strong
Spend conservation rate and improve 9.3%, modulus conservation rate improves 19.6%, and anti-light degradation capability improves.
Compared with unmodified aramid III fiber, the tensile strength of modifying aramid fiber III fibers improves 3.42%, and modulus carries
High by 0.6%, mechanical property also improves simultaneously.
Claims (10)
1. utilize supercritical CO2The method that fluid technique carries out the inorganization modification of aramid fiber, it is characterised in that step includes：
Step 1), aramid fiber and the supercritical CO dissolved with inorganic light stabilizer presoma2Fluid carries out swelling reaction, obtains
Aramid fiber containing inorganic light stabilizer presoma；
Step 2), the aramid fiber containing inorganic light stabilizer presoma is placed in alkaline alcohol solution or acidity alcohol solution, heat
Decompose modification of aramid fiber of the generation containing inorganic light stabilizer.
2. according to the method for claim 1, it is characterised in that in step 1), first by aramid fiber and inorganic light stabilizer
Presoma is placed in reaction vessel, and aramid fiber does not contact with inorganic light stabilizer presoma；Again dioxy is passed through to reaction vessel
Change carbon gas to generating supercritical carbon dioxide fluid；Supercritical carbon dioxide fluid carries the inorganic light stabilizer forerunner of dissolving
Body, swelling reaction is carried out with aramid fiber, obtain the aramid fiber containing inorganic light stabilizer presoma.
3. according to the method for claim 2, it is characterised in that in step 1), reaction vessel be passed through carbon dioxide it
Before, first carry out exhaust outlet processing.
4. according to the method for claim 2, it is characterised in that in step 1), aramid fiber be p-aramid fiber Kevlar,
Nomex fibers, Twaron fibers, Technora fibers, aramid III fiber or F-12 fibers；Inorganic light stabilizer presoma is
Nano-TiO 2 precursor or nanometer zinc oxide precursor, the addition of inorganic light stabilizer presoma is the titanium dioxide being passed through
The 1%~10% of carbonaceous amount, the addition of inorganic light stabilizer presoma are the 15%~60% of aramid fiber quality.
5. method according to claim 1 or 2, it is characterised in that in step 1), the generation of supercritical carbon dioxide fluid
Condition is 50~160 DEG C of temperature, 7~28Mpa of pressure.
6. method according to claim 1 or 2, it is characterised in that in step 1), be swelled time of reaction for 20~
120min。
7. according to the method for claim 4, it is characterised in that nano-TiO 2 precursor be titanium tetrachloride, metatitanic acid just
Butyl ester or iso-butyl titanate, nanometer zinc oxide precursor are hydration zinc acetate, zinc nitrate or zinc chloride.
8. method according to claim 1 or 2, it is characterised in that the aramid fiber containing inorganic light stabilizer presoma
In, inorganic light stabilizer presoma accounts for the 1%~10% of aramid fiber quality.
9. according to the method for claim 1, it is characterised in that in step 2), alkaline alcohol solution pH=7~10 are alkaline molten
Matter is hydrazine hydrate, ammoniacal liquor, NaOH or KOH；The concentration of acid solute is 0.2~1mol/L in acidity alcohol solution, and acid solute is
Hydrochloric acid or acetic acid；Alcoholic solvent is ethanol or propyl alcohol.
10. according to the method for claim 1, it is characterised in that in step 2), thermally decompose and thermally decomposed for backflow, 80~120
DEG C backflow thermal decomposition 1~3h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108442099A (en) * | 2018-03-28 | 2018-08-24 | 南通大学 | A kind of anti-ultraviolet nano zinc oxide composite textile and preparation method thereof |
| CN115652626A (en) * | 2022-09-08 | 2023-01-31 | 浙江英玛特生物科技有限公司 | SCF technology-based water-soluble fiber antibacterial processing method and product thereof |
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| CN102587131A (en) * | 2012-02-17 | 2012-07-18 | 东华大学 | Method for modifying interior and surface of aramid fiber through isocyanate in supercritical CO2 |
| CN103469602A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for improving mechanical properties of aramid fiber in supercritical fluid through stretching orientation |
| CN103469573A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for improving mechanical property of aramid fiber in supercritical fluid through stretching orientation and chemical crosslinking |
| CN106243786A (en) * | 2016-07-29 | 2016-12-21 | 贵州大学 | A kind of preparation method of the fabric ultraviolet resistant of simple and efficient |
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|---|---|---|---|---|
| CN102587131A (en) * | 2012-02-17 | 2012-07-18 | 东华大学 | Method for modifying interior and surface of aramid fiber through isocyanate in supercritical CO2 |
| CN103469602A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for improving mechanical properties of aramid fiber in supercritical fluid through stretching orientation |
| CN103469573A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for improving mechanical property of aramid fiber in supercritical fluid through stretching orientation and chemical crosslinking |
| CN106243786A (en) * | 2016-07-29 | 2016-12-21 | 贵州大学 | A kind of preparation method of the fabric ultraviolet resistant of simple and efficient |
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| CN108442099A (en) * | 2018-03-28 | 2018-08-24 | 南通大学 | A kind of anti-ultraviolet nano zinc oxide composite textile and preparation method thereof |
| CN108442099B (en) * | 2018-03-28 | 2020-06-02 | 南通大学 | Anti-ultraviolet nano zinc oxide composite textile fabric and preparation method thereof |
| CN115652626A (en) * | 2022-09-08 | 2023-01-31 | 浙江英玛特生物科技有限公司 | SCF technology-based water-soluble fiber antibacterial processing method and product thereof |
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