CN107385878B - By using supercritical CO2Method for performing inorganic modification on aramid fiber by using fluid technology - Google Patents
By using supercritical CO2Method for performing inorganic modification on aramid fiber by using fluid technology Download PDFInfo
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- 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 System; Titanates; Zirconates; Stannates; Plumbates
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- 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 System; Zincates; Cadmates
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- 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
Abstract
The invention relates to the utilization of supercritical CO2The method for performing inorganic modification on aramid fiber by using a fluid technology comprises the following steps: step 1), aramid fiber and supercritical CO dissolved with inorganic light stabilizer precursor2Carrying out swelling reaction on the fluid to obtain aramid fibers containing inorganic light stabilizer precursors; and 2), placing the aramid fiber containing the inorganic light stabilizer precursor into an alcohol solvent containing an alkaline solute or an acidic solute, and thermally decomposing to generate the modified aramid fiber containing the inorganic light stabilizer. The invention utilizes supercritical CO2The liquid has strong permeation and carrying effects, and carries the small-molecular light stabilizer precursor to enter the amorphous areas on the surface and inside the aramid fiber, so that on one hand, the mechanical property of the fiber is improved by utilizing the plasticizing effect of the supercritical carbon dioxide, and on the other hand, the structure of the nano light stabilizer in the amorphous areas can be controlled, agglomeration is avoided, and the photodegradation resistance of the fiber is improved.
Description
Technical Field
The invention belongs to the field of fiber modification, and particularly relates to a method for utilizing supercritical CO2A method for performing inorganic modification on aramid fibers by a fluid technology.
Background
Aramid fiber is high-performance fiber containing aromatic rigid chains with benzene rings more than 85 percent, has excellent performances of high strength, high modulus, high temperature resistance, chemical solvent resistance, small specific gravity and the like, is widely applied to advanced strategic weapons, such as the fields of space engines, soldier bulletproof protection devices, aerospace, automobiles, optical fiber reinforcement, cables and the like, and is an important strategic substance.
The aramid fiber is internally composed of highly oriented crystalline regions and amorphous regions, the amorphous regions are partially composed of microfibers and micropores, and the breakage of the fiber generally occurs in the amorphous regions first. The aramid fiber contains a large number of C-N bonds and double bonds in a molecular chain, and is easy to absorb ultraviolet light with the wavelength of 300-450 nm and partial visible light, and the defects of photoaging degradation, fiber brittleness and color change, surface cracks and the like can occur under the aerobic environment and ultraviolet light irradiation for a long time, so that the mechanical property of the aramid fiber product is gradually reduced, the service life of the fiber is influenced, and the application of the aramid fiber is restricted. The aramid fiber has poor photodegradation resistance, influences the service life of products applied outdoors and in aerospace, more importantly influences the use safety of products such as bulletproof and the like, and is a long-term unsolved technological problem.
In the prior art, the surface of the aramid fiber is modified and covered to protect the fiber from being damaged by ultraviolet light and visible light, and specifically, a substance containing an ultraviolet light stabilizer or a protective layer containing a light stabilizer, such as SiO, is coated on the surface of the fiber2、 TiO2ZnO, etc., but because the fiber surface is relatively smooth, there are few functional groups that can react, the photodegradation-resistant protective layer can only adhere to the fiber surface, and the adhesion is poor. The photodegradation-resistant substances coated on the surface can not completely block the invasion of ultraviolet rays, and the amorphous region in the aramid fiber is still sensitive to weak ultraviolet rays and is easily photodegraded due to the fact that the amorphous region contains a large number of end groups which are easily photodegraded, and particularly after the photodegradation-resistant substances fall off, the amorphous region of the aramid fiber is easily photodegradation-aged.
Therefore, how to introduce the light stabilizer into the fiber, especially into the amorphous area inside the fiber, overcomes the problems of poor surface covering stability, weak photolysis resistance, large application limitation of the modification method and the like caused by the surface modification covering of the fiber, improves the photodegradation resistance of the fiber without reducing the mechanical property of the fiber, and still needs to further solve the technical problem.
Disclosure of Invention
In response to the deficiencies of the prior art, the present invention provides for the utilization of supercritical CO2A method for performing inorganic modification on aramid fibers by a fluid technology.
The technical scheme of the invention is as follows: by using supercritical CO2The method for performing the inorganic modification of the aramid fiber by the fluid technology comprises the following steps:
step 1), aramid fiber and supercritical CO dissolved with inorganic and organic light stabilizer precursors2Carrying out swelling reaction on the fluid to obtain aramid fibers containing inorganic light stabilizer precursors;
and 2) placing the aramid fiber containing the inorganic light stabilizer precursor into an alkaline alcohol solution or an acidic alcohol solution, and thermally decomposing to generate the modified aramid fiber containing the inorganic light stabilizer.
In the step 1), aramid fiber and an inorganic light stabilizer precursor are placed in a reaction container, and the aramid fiber is not in contact with the inorganic light stabilizer precursor; then introducing carbon dioxide gas into the reaction vessel until supercritical carbon dioxide fluid is generated; carrying the dissolved inorganic light stabilizer precursor by the supercritical carbon dioxide fluid, and carrying out swelling reaction with the aramid fiber to obtain the aramid fiber containing the inorganic light stabilizer precursor. The swelling reaction means that a light stabilizer carried by supercritical carbon dioxide is contacted with the aramid fiber in a solvent wetting mode.
In the step 1), before introducing carbon dioxide gas into the reaction container, carrying out exhaust and drainage treatment. Specifically, the treatment mode of exhaust and drainage is that the reaction container is heated until the moisture is converted into water vapor; and then carrying out vacuum-pumping treatment on the reaction container. The purpose of the exhaust and drainage treatment is to eliminate air and moisture in the closed container and eliminate the influence of active gases such as oxygen and moisture in the air on the experiment.
In the step 1), the aramid fiber is para-aramid Kevlar, Nomex fiber, Twaron fiber, Technora fiber, ArIII fiber or F-12 fiber, the precursor of the inorganic light stabilizer is a nano titanium dioxide precursor or a nano zinc oxide precursor, the addition amount of the precursor of the inorganic light stabilizer is 1-10% of the mass of the introduced carbon dioxide, and preferably, the addition amount of the precursor of the inorganic light stabilizer is 2.5-5% of the mass of the introduced carbon dioxide; the adding amount of the inorganic light stabilizer precursor is 15-60% of the mass of the aramid fiber, and preferably, the adding amount of the inorganic light stabilizer precursor is 20-50% of the mass of the aramid fiber.
In the step 1), the supercritical carbon dioxide fluid is generated under the conditions of 50-160 ℃ and 7-28 Mpa. Due to the temperature being CO2An important index of the supercritical fluid state is that the CO can be realized only when the temperature is more than 31 ℃ and certain pressure is matched2And temperature and pressure affect CO2The concentration in the high-pressure reaction kettle further influences the concentration of the light stabilizer precursor. PreferablyThe supercritical carbon dioxide fluid is generated under the conditions of 50-100 ℃ and 10-15 Mpa.
The reaction vessel is heated by electrical heating or oil bath heating.
In the step 1), the swelling reaction time is 20-120 min. Preferably, the swelling reaction time is 30-90 min.
In the step 1), after the swelling reaction is finished, the pressure of the reaction vessel is released. Specifically, the pressure relief time is 1-10 min, and preferably 1-5 min.
The precursor of the nano titanium dioxide is titanium tetrachloride, n-butyl titanate or isobutyl titanate, and the precursor of the nano zinc oxide is hydrated zinc acetate, zinc nitrate or zinc chloride.
In the aramid fiber containing the inorganic light stabilizer precursor, the inorganic light stabilizer precursor accounts for 1-10% of the mass of the aramid fiber. Preferably, the inorganic light stabilizer precursor accounts for 1.5-7% of the mass of the aramid fiber.
In the step 1), the aramid fiber is cleaned and dried, specifically, the aramid fiber is placed in an organic solvent, and is subjected to constant-temperature ultrasonic washing and vacuum drying. The organic solvent is acetone, the ultrasonic temperature is 60-95 ℃, and the ultrasonic time is 1-2 h; the drying temperature is 70-100 ℃, and the drying time is 1-8 h. Preferably, the ultrasonic temperature is 75-85 ℃, and the ultrasonic time is 1-1.2 h; the drying temperature is 75-85 ℃, and the drying time is 1-2 h.
In the step 2), when the precursor of the inorganic light stabilizer is a precursor of nano zinc oxide, the alcoholic solution is an alkaline alcoholic solution.
In the step 2), the pH of an alkaline alcoholic solution is 7-10, the alkaline solute is hydrazine hydrate, ammonia water, NaOH or KOH, preferably, the pH of the alkaline alcoholic solution is 8-9, and the alkaline solute is KOH; the concentration of the acidic solute in the acidic alcohol solution is 0.2-1 mol/L, the acidic solute is hydrochloric acid or acetic acid, preferably, the concentration of the acidic solute in the acidic alcohol solution is 0.25-0.9 mol/L, and the acidic solute is acetic acid.
In the step 2), the thermal decomposition is reflux thermal decomposition, and the reflux thermal decomposition is carried out for 1-3 h at the temperature of 80-120 ℃. Preferably, the reflux thermal decomposition is carried out for 1.5 to 2.5 hours at the temperature of 85 to 100 ℃.
In the step 2), the modified aramid fiber is cleaned and dried, and specifically, the modified aramid fiber is placed in an organic solvent, washed at a constant temperature to a constant weight and then dried in vacuum. The organic solvent is acetone, ethanol or methanol, the washing temperature is 60-95 ℃, the drying temperature is 70-120 ℃, and the drying time is 1-2 h. Preferably, the organic solvent is acetone, the washing temperature is 75-85 ℃, the drying temperature is 75-100 ℃, and the drying time is 1-1.2 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the aramid fiber has higher crystallinity and a rigid molecular chain structure with regular arrangement, so that common compounds are difficult to permeate into the fiber, and supercritical CO (carbon monoxide)2The fluid has strong permeation and carrying effects, and can carry small molecular compounds into aramid fibers, particularly amorphous regions in the fibers.
2. The invention utilizes supercritical CO2The fluid technology brings the light stabilizer precursor micromolecules into the amorphous areas on the surface and inside of the aramid fiber, the light stabilizer precursor introduced into the amorphous areas on the surface and inside of the fiber is converted into the light stabilizer through the thermal decomposition, and the amorphous areas of the aramid fiber are in the nanometer-micrometer scale, so that the nanometer light stabilizer can be formed in the amorphous areas, and the nanometer light stabilizer has a controllable structure, does not agglomerate, and improves the light degradation resistance of the fiber. Meanwhile, the nano light stabilizer formed in the amorphous region of the aramid fiber further improves the mechanical property of the aramid fiber. And the nanometer light stabilizer is firmly combined with the amorphous area, so that the nanometer light stabilizer is not separated, and the photodegradation resistance and the mechanical property are kept effective for a long time.
3. After the aging treatment for 7 days by ultraviolet irradiation, compared with unmodified aramid fibers, the strength retention rate of the modified aramid fibers is improved by 9.3-26.7%, the modulus retention rate of the aramid fibers is improved by 4.4-19.6%, and the photodegradation resistance of the modified aramid fibers is obviously improved.
4. Compared with unmodified aramid fibers, the tensile strength of the modified aramid fibers is improved by 2.24-11.54%, the modulus is improved by 0.6-5.15%, namely, the mechanical properties of the modified aramid fibers are improved while the photodegradation resistance is improved.
5. The invention utilizes supercritical CO2The method for carrying out inorganic modification on aramid fibers by using the fluid technology has the advantages of economy, environmental protection, controllable reaction, simple separation of solvent and products, little influence on the mechanical properties of the fibers and the like, and has great industrial application value.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Placing 5g Kevlar49 fiber into acetone solvent, ultrasonic washing at 80 deg.C for 1h, taking out, and vacuum drying at 80 deg.C for 2 h.
(2) The washed and dried Kevlar49 fiber obtained in step (1) and 2g of n-butyl titanate were placed in a 2L autoclave, and the Kevlar49 fiber was placed on a metal holder so as not to contact the n-butyl titanate.
(3) Heating a 2L high-pressure reaction kettle to 100 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air and water in the kettle, and filling CO into the kettle after the temperature in the kettle is reduced to 80 DEG C2The pressure in the kettle reaches 10Mpa and is in supercritical CO2The mass of the n-butyl titanate is 3 percent of the mass of the carbon dioxide in the reaction kettle; after swelling reaction for 40min, the pressure in the reactor was relieved to normal pressure for 3min to obtain Kevlar49 fiber containing 0.17g of n-butyl titanate.
(4) Kevlar49 fiber containing 0.17g of n-butyl titanate was placed in 50mL of an ethanolic acetate solution with an acetic acid concentration of 0.29mol/L and refluxed at 85 ℃ for 2 hours to obtain modified Kevlar49 fiber.
(5) The modified Kevlar49 fiber was washed with acetone at 80 ℃ for 1 hour to constant weight and then dried under vacuum at 80 ℃ for 1 hour. .
(6) The mechanical properties of Kevlar49 fiber, modified Kevlar49 fiber, aged Kevlar49 fiber and aged modified Kevlar49 fiber were tested by a monofilament strength tester, and the aging treatment method was: the Kevlar49 fibers and modified Kevlar49 fibers were exposed to accelerated uv light for 7 days for aging tests.
The monofilament tensile strength of the Kevlar49 fiber is 22.3CN/dtex, and the modulus is 780.4 CN/dtex; the tensile strength of the aged Kevlar49 fiber was 10CN/dtex, the strength retention was 45.4%, the modulus was 460.5CN/dtex, and the modulus retention was 58.9%.
The tensile strength of the modified Kevlar49 fiber is 22.8CN/dtex, and the modulus is 790.6 CN/dtex; the modified Kevlar49 fiber after aging treatment had a tensile strength of 16.5CN/dtex, a strength retention of 72.1%, a modulus of 620.4CN/dtex, and a modulus retention of 78.5%. Compared with Kevlar49 fiber which is not modified, the mechanical property is improved, and the light degradation resistance is improved.
Compared with Kevlar49 fiber which is not modified, the tensile strength retention rate of the modified Kevlar49 fiber is improved by 26.7%, the modulus retention rate is improved by 19.6%, and the photodegradation resistance is improved through aging experiments.
Compared with unmodified Kevlar49 fiber, the modified Kevlar49 fiber has the advantages of 2.24% improved tensile strength, 1.3% improved modulus and improved mechanical properties.
Example 2
(1) Placing 5.5g Kevlar29 fiber into acetone solvent, ultrasonically washing at 80 ℃ for 1h, taking out, and vacuum drying at 80 ℃ for 2 h.
(2) The washed and dried Kevlar29 fiber obtained in step (1) and 2.5g of titanium tetrachloride were placed in a 2L autoclave, and the Kevlar29 fiber was placed on a metal holder so as not to contact titanium tetrachloride.
(3) Heating a 2L high-pressure reaction kettle to 100 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air and water in the kettle, and filling CO into the kettle after the temperature in the kettle is reduced to 80 DEG C2The pressure in the kettle reaches 10Mpa and is in supercritical CO2In the state, the mass of the titanium tetrachloride is 2.5 percent of the mass of the carbon dioxide in the reaction kettle; after the swelling reaction was carried out for 40min, the pressure in the reactor was released to normal pressure for 5min to obtain Kevlar29 fiber containing 0.1g of titanium tetrachloride.
(4) Kevlar29 fiber containing 0.1g titanium tetrachloride was placed in 50mL of acetic acid propanol solution with an acetic acid concentration of 0.86mol/L and refluxed at 95 ℃ for 1.5 hours to obtain modified Kevlar29 fiber.
(5) The modified Kevlar29 fiber was washed with acetone at 80 ℃ for 1 hour to constant weight and then dried under vacuum at 80 ℃ for 1 hour. .
(6) The mechanical properties of Kevlar29 fiber, modified Kevlar29 fiber, aged Kevlar29 fiber and aged modified Kevlar29 fiber were tested by a monofilament strength tester, and the aging treatment method was: the Kevlar29 fibers and modified Kevlar29 fibers were exposed to accelerated uv light for 7 days for aging tests.
The monofilament tensile strength of the Kevlar29 fiber is 20.1CN/dtex, and the modulus is 480.2 CN/dtex; the tensile strength of the aged Kevlar fiber is 11.5CN/dtex, the strength retention rate is 57.2 percent, the modulus is 338.5CN/dtex, and the modulus retention rate is 70.5 percent.
The tensile strength of the modified Kevlar29 fiber is 20.9CN/dtex, and the modulus is 490.6 CN/dtex; the modified Kevlar29 fiber after aging treatment had a tensile strength of 17.5CN/dtex, a strength retention of 83.7%, a modulus of 430.2CN/dtex, and a modulus retention of 87.8%. Compared with Kevlar29 fiber which is not modified, the mechanical property is improved, and the light degradation resistance is improved.
Compared with Kevlar29 fiber which is not modified, after aging experiments, the tensile strength retention rate of the modified Kevlar29 fiber is improved by 26.5%, the modulus retention rate is improved by 17.3%, and the photodegradation resistance is improved.
Compared with unmodified Kevlar29 fiber, the modified Kevlar29 fiber has the advantages of 3.98% improved tensile strength, 2.16% improved modulus and improved mechanical properties.
Example 3
(1) 6g Tecnora fiber is put into an acetone solvent, ultrasonically washed for 1h at 80 ℃, taken out, and vacuum dried for 2h at 80 ℃.
(2) The Tecnora fibers washed and dried in step (1) and 1.2g of titanium tetrachloride were placed in a 2L autoclave, and the Tecnora fibers were placed on a metal holder so as not to contact titanium tetrachloride.
(3) By means of an oil bathHeating 2L high-pressure reaction kettle to 100 deg.C, vacuumizing to remove air and water in the kettle, cooling to 70 deg.C, and charging CO into the kettle2The pressure in the kettle reaches 13Mpa and is in supercritical CO2In the state, the mass of the titanium tetrachloride is 3.5 percent of the mass of the carbon dioxide in the reaction kettle; after the swelling reaction is carried out for 60min, the pressure in the reaction kettle is discharged to normal pressure for 3min, and Tecnora fiber containing 0.2g of titanium tetrachloride is obtained.
(4) And (3) placing the Tecnora fiber containing 0.2g of titanium tetrachloride in 50mL of potassium hydroxide ethanol solution with the pH value of 8-9, and refluxing for 2h at 90 ℃ to obtain the modified Tecnora fiber.
(5) The modified Tecnora fiber is washed by acetone at 80 ℃ for 1h to constant weight and then dried in vacuum at 80 ℃ for 1 h. .
(6) The mechanical properties of the Tecnora fiber, the modified Tecnora fiber, the aged Tecnora fiber and the aged modified Tecnora fiber are tested by using a monofilament strength tester, and the aging treatment method comprises the following steps: the aging tests were performed by exposing the Tecnora fibers and the modified Tecnora fibers to light under accelerated ultraviolet light for 7 days.
The monofilament tensile strength of the Tecnora fiber is 20.2CN/dtex, and the modulus is 520.4 CN/dtex; the tensile strength of the aged Tecnora fiber is 9.2CN/dtex, the strength retention rate is 45.4 percent, the modulus is 410.5CN/dtex, and the modulus retention rate is 78.9 percent.
The tensile strength of the modified Tecnora fiber is 20.8CN/dtex, and the modulus is 540.6 CN/dtex; the modified Tecnora fiber after aging treatment has the tensile strength of 8.5CN/dtex, the strength retention rate of 40.9 percent, the modulus of 450.4CN/dtex and the modulus retention rate of 83.3 percent. Compared with the Tecnora fiber which is not modified, the mechanical property of the fiber is improved, and the photodegradation resistance is improved.
Compared with the Tecnora fiber which is not modified, after aging experiments, the modulus retention rate of the modified Tecnora fiber is improved by 4.4%, and the photodegradation resistance is improved.
Compared with the unmodified Tecnora fiber, the modified Tecnora fiber has the advantages that the tensile strength is improved by 2.97%, the modulus is improved by 3.88%, and the mechanical property is also improved.
Example 4
(1) Putting 4.8g of Nomex fiber into an acetone solvent, ultrasonically washing for 1h at 80 ℃, taking out, and vacuum drying for 2h at 80 ℃.
(2) Placing the washed and dried Nomex fiber obtained in the step (1) and 1.2g of anhydrous zinc acetate in a 2L high-pressure reaction kettle, and placing the Nomex fiber on a metal frame so that the Nomex fiber is not contacted with the anhydrous zinc acetate.
(3) Heating a 2L high-pressure reaction kettle to 100 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air and water in the kettle, and filling CO into the kettle2The pressure in the kettle reaches 13Mpa and is in supercritical CO2In the state, the mass of the anhydrous zinc acetate is 3 percent of the mass of the carbon dioxide in the reaction kettle; after swelling reaction for 90min, discharging the pressure in the reaction kettle to normal pressure for 4min to obtain the Nomex fiber containing 0.3g of anhydrous zinc acetate.
(4) And (3) placing the Nomex fiber containing 0.3g of anhydrous zinc acetate in 60mL of potassium hydroxide ethanol solution with the pH value of 8-9, and refluxing for 2h at 90 ℃ to obtain the modified Nomex fiber.
(5) The modified Nomex fibers were cleaned with acetone at 80 ℃ for 1h to constant weight and then vacuum dried at 80 ℃ for 1 h. .
(6) Testing the mechanical properties of the Nomex fiber, the modified Nomex fiber, the aged Nomex fiber and the aged modified Nomex fiber by using a monofilament strength tester, wherein the aging treatment method comprises the following steps: the Nomex fibers and modified Nomex fibers were exposed to accelerated uv light for 7 days for aging tests.
The monofilament tensile strength of the Nomex fiber is 5.2CN/dtex, and the modulus is 120.4 CN/dtex; the tensile strength of the aged Nomex fiber is 3.2CN/dtex, the strength retention rate is 61.5 percent, the modulus is 80.5CN/dtex, and the modulus retention rate is 66.8 percent.
The tensile strength of the modified Nomex fiber is 5.8CN/dtex, and the modulus is 126.6 CN/dtex; the modified Nomex fiber after aging treatment has the tensile strength of 4.8CN/dtex, the strength retention rate of 82.7 percent, the modulus of 100.6CN/dtex and the modulus retention rate of 83.6 percent. Compared with Nomex fiber which is not modified, the mechanical property of the Nomex fiber is improved, and the photodegradation resistance of the Nomex fiber is improved.
Compared with Nomex fibers which are not modified, after aging experiments, the tensile strength retention rate of the modified Nomex fibers is improved by 21.2%, the modulus retention rate is improved by 16.8%, and the photodegradation resistance is improved.
Compared with the unmodified Nomex fiber, the modified Nomex fiber has the advantages that the tensile strength is improved by 11.54 percent, the modulus is improved by 5.15 percent, and the mechanical property is also improved.
Example 5
(1) Putting 6g of aramid fiber III into an acetone solvent, ultrasonically washing for 1h at 80 ℃, taking out, and vacuum drying for 2h at 80 ℃.
(2) And (2) placing the washed and dried aramid fiber III in the step (1) and 1.2g of anhydrous zinc chloride in a 2L high-pressure reaction kettle, and placing the aramid fiber III on a metal frame so as not to contact the anhydrous zinc chloride.
(3) Heating a 2L high-pressure reaction kettle to 100 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air and water in the kettle, and then filling CO into the kettle2The pressure in the kettle reaches 13Mpa and is in supercritical CO2In the state, the mass of the anhydrous zinc chloride is 5 percent of the mass of the carbon dioxide in the reaction kettle; after swelling reaction for 90min, discharging the pressure in the reaction kettle for 5min to normal pressure to obtain the aramid fiber III containing 0.3g of anhydrous zinc chloride.
(4) And (3) placing the aramid fiber III containing 0.3g of anhydrous zinc chloride in 60mL of potassium hydroxide ethanol solution with the pH value of 8-9, and refluxing for 2h at 90 ℃ to obtain the modified aramid fiber III.
(5) And cleaning the modified aramid fiber III with acetone at 80 ℃ for 1h to constant weight, and then carrying out vacuum drying at 80 ℃ for 1 h. .
(6) The mechanical properties of aramid fiber III, modified aramid fiber III, aramid fiber III subjected to aging treatment and aramid fiber III subjected to aging treatment are tested by using a monofilament strength tester, and the aging treatment method comprises the following steps: and (3) placing the aramid fiber III and the modified aramid fiber III under the accelerated ultraviolet light for illumination for 7 days for an aging test.
The monofilament tensile strength of the aramid fiber III is 29.2CN/dtex, and the modulus is 1020.4 CN/dtex; the aramid III fiber after aging treatment has the tensile strength of 23.2CN/dtex, the strength retention rate of 79.4 percent, the modulus of 680.5CN/dtex, and the modulus retention rate of 66.9 percent.
The tensile strength of the modified aramid fiber III is 30.2CN/dtex, and the modulus is 1026.6 CN/dtex; the modified aramid III fiber after aging treatment has the tensile strength of 26.8CN/dtex, the strength retention rate of 88.7 percent, the modulus of 883.4CN/dtex, and the modulus retention rate of 86.5 percent. Compared with the aramid fiber III without modification treatment, the mechanical property is improved, and the photodegradation resistance is improved.
Compared with the aramid fiber III without modification treatment, after aging experiments, the tensile strength retention rate of the modified aramid fiber III is improved by 9.3%, the modulus retention rate is improved by 19.6%, and the photodegradation resistance is improved.
Compared with unmodified aramid fiber III, the tensile strength of the modified aramid fiber III is improved by 3.42 percent, the modulus is improved by 0.6 percent, and the mechanical property is also improved.
Claims (3)
1. By using supercritical CO2The method for performing inorganic modification on aramid fibers by using a fluid technology is characterized by comprising the following steps of:
step 1), firstly, placing aramid fiber and an inorganic light stabilizer precursor into a reaction container, wherein the aramid fiber is not in contact with the inorganic light stabilizer precursor; then introducing carbon dioxide gas into the reaction vessel until supercritical carbon dioxide fluid is generated; carrying the dissolved inorganic light stabilizer precursor by supercritical carbon dioxide fluid, and carrying out swelling reaction with aramid fiber for 30-90 min to obtain the aramid fiber containing the inorganic light stabilizer precursor;
the aramid fiber is para-aramid Kevlar, Nomex fiber, Twaron fiber, Technora fiber, aramid III fiber or F-12 fiber; the inorganic light stabilizer precursor is a nano titanium dioxide precursor or a nano zinc oxide precursor, and the addition amount of the inorganic light stabilizer precursor is 2.5-5% of the mass of the introduced carbon dioxide; the precursor of the nano titanium dioxide is titanium tetrachloride, n-butyl titanate or isobutyl titanate, and the precursor of the nano zinc oxide is hydrated zinc acetate, zinc nitrate or zinc chloride; in the aramid fiber containing the inorganic light stabilizer precursor, the inorganic light stabilizer precursor accounts for 1.5-7% of the mass of the aramid fiber;
step 2), placing the aramid fiber containing the inorganic light stabilizer precursor into an alkaline alcohol solution or an acidic alcohol solution, and thermally decomposing to generate modified aramid fiber containing the inorganic light stabilizer; the thermal decomposition conditions were: refluxing and thermally decomposing for 1-3 h at 80-120 ℃;
the pH of the alkaline alcoholic solution is = 7-10, and the alkaline solute is hydrazine hydrate, ammonia water, NaOH or KOH; the concentration of an acidic solute in the acidic alcohol solution is 0.2-1 mol/L, and the acidic solute is hydrochloric acid or acetic acid; the alcohol solvent is ethanol or propanol.
2. The method as claimed in claim 1, wherein in the step 1), before the carbon dioxide gas is introduced into the reaction vessel, the exhaust water is treated.
3. The method according to claim 1 or 2, wherein the supercritical carbon dioxide fluid is produced at a temperature of 50 to 160 ℃ and a pressure of 7 to 28MPa in step 1).
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