Agilawood-containing regenerated cellulose fiber and preparation method thereof

Abstract

The invention discloses a regenerated cellulose fiber containing agilawood and a preparation method thereof, and relates to the technical field of cellulose fibers. According to the invention, the modified agilawood fiber is utilized to reinforce the regenerated cellulose matrix to prepare the high-strength and high-toughness fiber. The modified agilawood fiber is subjected to silver ion modification and aldehyde group treatment, and when the modified agilawood fiber is mixed with the secondary modified tourmaline, the peel powder assists in reducing the silver ions, so that nano-silver is loaded on the surface of the fiber, and good antibacterial performance is shown under the combined action. Large-particle-size porous tourmaline is used, and 4-hydroxycrotonic acid is combined for grinding modification, so that the tourmaline is combined with regenerated cellulose, and the fiber strength is enhanced. Through secondary grinding modification of the nanoscale pericarp powder, tourmaline holes are filled, the activity of the pericarp powder is improved, and the pericarp powder is loaded in tourmaline. The modified tourmaline and the agilawood fibers are mixed and combined through chemical bonds, the fibers are curled to wrap the pericarp powder under the ultrasonic action, spinning and washing losses are reduced, and the long-acting fragrance and deodorization effect of the fibers are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of cellulose fibers, and particularly to a regenerated cellulose fiber containing agarwood and a preparation method thereof. Background Art

[0002] With the improvement of living standards, the public not only pays attention to the appearance and sensory properties of commodities, such as packaging, smell, color, shape, etc., but also increasingly attaches importance to the health of themselves and their families. People begin to worry about the problem of bacterial growth in fiber woven or non-woven products in daily life. Therefore, it is particularly necessary to develop a natural antibacterial fiber with fragrance and its products. Different fragrances have different effects on the human body, and they can provide multiple functions such as physiotherapy, insect repellent, antibacterial, etc., and keep the surface clean.

[0003] Currently, the main method for aromatic fabrics is post-treatment. The essence is encapsulated in a polymer film to form aromatic microcapsules, which are then sprayed onto the fiber surface and heat-set. However, when the aromatic chemical fiber obtained by this method is made into a fabric, the uniformity is poor, it is not wash-resistant, the wash-resistant performance is poor, the fragrance retention time of the aromatic fabric is short, and the aromatic effect is not satisfactory. Generally, the fragrance will be lost after washing 10 - 20 times. Agarwood fiber is an important component of agarwood. During the extraction process of agarwood essential oil, the insoluble agarwood fiber is often regarded as waste and lacks effective utilization. These agarwood fibers still retain the unique flavor of agarwood, so they have certain application prospects in the field of aromatic fibers. Summary of the Invention

[0004] The purpose of the present invention is to provide a regenerated cellulose fiber containing agarwood and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A preparation method of a regenerated cellulose fiber containing agarwood, which is characterized by comprising the following preparation steps:

[0006] (1) Add porous tourmaline balls with a particle size of 0.1 - 1 mm into the ball mill tank, add 4 - hydroxycrotonic acid and zirconia balls, first ball mill for 0.5 - 2 h, then add an initiator into the tank, and continue to ball mill for 0.5 - 0.6 h under the protection of inert gas. Take out 1 / 2 to obtain the first modified tourmaline, and grind the remaining 1 / 2 to a particle size of 300 - 500 nm, and freeze-dry at -30°C for 6 h to obtain modified tourmaline nanoflour;

[0007] (2) After freeze-drying 0.8 - 1.2 parts by mass of the first modified tourmaline at -30°C for 6 h, add 0.1 - 0.6 parts by mass of peel powder with a particle size of 10 - 20 nm, and ball mill for 20 - 40 min to obtain the second modified tourmaline;

[0008] (3) Disperse the secondarily modified tourmaline in soft water, add aldehyde-group-containing agarwood fibers under 20 kHz ultrasonic waves to obtain a dispersion with a solid content of 50 wt%, add a silver ammonia solution with a volume 0.25 times that of the soft water, heat and react in a water bath at 90 °C for 0 - 2 h, drain, and freeze-dry at -18 °C for 12 h to obtain modified agarwood fibers;

[0009] (4) Mix 30 - 50 parts by mass of regenerated cellulose spinning dope, 10 - 20 parts by mass of modified tourmaline nanopowder, and 30 - 50 parts by mass of ordinary spinning sizing solution, stir at 500 rpm for 10 min, then add 10 - 20 parts by mass of modified agarwood fibers, and obtain regenerated cellulose fibers containing agarwood through degassing and spinning.

[0010] Further, the preparation method of the porous tourmaline balls in step (1) is as follows: Mix 100 parts by mass of 1 - 3 μm tourmaline and 15 - 30 parts by mass of 1 - 3 μm low-melting-point powder to form a mixture. Then, mix dextrin and water at 80 °C in a mass ratio of 1:8.5 - 10 to form a mixed solution. Add the mixed solution to the mixture, with the mass ratio of tourmaline to dextrin being 85:9, mix and stir until it becomes a muddy state, pour it into a mold, dry, and sinter at 650 - 750 °C to prepare porous tourmaline balls with a particle size of 0.1 - 1 mm; the mass fractions of each component of the low-melting-point powder are: ZnO: 15 - 18 parts; H3BO4: 15 - 18 parts; SiO2: 30 - 40 parts; Al2O3: 10 - 12 parts; K2CO3: 10 - 15 parts; Na2CO3: 10 - 12 parts; the pore diameter of the mesoporous material of the porous tourmaline balls is between 2 - 50 nm, and the specific surface area is above 600 m 2 / g.

[0011] Further, the mass ratio of the tourmaline powder, 4-hydroxycrotonic acid, and peroxide initiator in step (1) is 100:20 - 40:5 - 10.

[0012] Further, during the ball milling process in step (1), control the rotation speed of the ball mill to be 300 - 500 r / min and the ball-to-material ratio to be 15:1.

[0013] Further, the initiator in step (1) is di-tert-butyl peroxide.

[0014] Further, the peel powder in step (2) is obtained by drying and pulverizing lemon peel or citrus peel.

[0015] Further, the particle size of the peel powder in step (2) is 10 - 20 nm.

[0016] Further, during the ball milling process in step (2), control the rotation speed of the ball mill to be 500 r / min and the ball-to-material ratio to be 20:1.

[0017] Further, the aldehyde group-containing agarwood fiber described in step (3) is prepared by oxidizing agarwood fiber with sodium periodate, and the agarwood fiber is a modified agarwood fiber prepared with reference to CN202411210130.8.

[0018] Further, the preparation method of the silver ammonia solution described in step (3) is as follows: Take 50 mL of 2 wt% AgNO3 aqueous solution, and gradually add 2 wt% ammonia water dropwise thereto while shaking until the initially formed precipitate just completely dissolves.

[0019] Further, the mass ratio of the aldehyde group-containing agarwood fiber to the secondarily modified tourmaline described in step (3) is 5:1.

[0020] Further, the methyl cellulose content of the ordinary spinning sizing solution described in step (4) is 9.4%, the viscosity is 42 S, and the alkali content is 5.3%.

[0021] Further, the regenerated cellulose spinning dope described in step (4) is a filtered regenerated spinning sizing solution prepared with reference to CN202010096086.8.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0023] (1) The present invention uses modified agarwood fiber as a reinforcing and toughening body, which interpenetrates with the regenerated cellulose matrix, making the prepared regenerated cellulose fiber high-strength and high-toughness. The modified agarwood fiber of the present invention is a silver ion-modified aldehyde group-containing agarwood fiber. During the mixing process with the secondarily modified tourmaline, the pericarp powder can be used as a co-reducing agent to assist the aldehyde group-containing agarwood fiber to reduce silver ions, so that nano-silver is loaded on the surface of the agarwood fiber, and together with the pericarp powder, an excellent antibacterial effect is achieved.

[0024] (2) The present invention uses large-particle-size porous tourmaline for grinding modification, and the grinding modifier is 4-hydroxycrotonic acid, which is grafted and coated on the surface of the porous tourmaline, can combine with the regenerated cellulose, fill the gaps between the structures of the regenerated cellulose, enhance the breaking strength of the regenerated cellulose fiber. At the same time, relatively large-particle-size microparticles during the grinding process are taken for the second grinding modification, and the second grinding modifier is nano-scale pericarp powder. Through reasonable ratio design, the nano-scale pericarp powder is affected by the grinding speed and external mechanical force and fills the pores of the tourmaline. And during the grinding process, the fibers in the pericarp powder are damaged, improving its activity, and then can be loaded inside the tourmaline. And the secondarily modified tourmaline and the modified agarwood fiber are preferentially mixed. The tourmaline and the modified agarwood fiber are combined by chemical bonds, and then the tourmaline is loaded on the fiber. Through ultrasonic action, the fiber is curled and then in a wrapped state, fixing the pericarp powder in the tourmaline, reducing subsequent spinning and washing losses, thereby improving the long-term fragrance and deodorization effects of the regenerated cellulose fiber. Specific Embodiments

[0025] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0026] Example 1

[0027] (1) Mix 100 parts by mass of 1 μm tourmaline and 15 parts by mass of 1 μm low melting point powder to form a mixture. Then, mix dextrin and water at 80 °C in a mass ratio of 1:8.5 to form a mixed solution. Add the mixed solution to the mixture. The mass ratio of tourmaline to dextrin is 85:9. Mix and stir until it becomes a muddy state, pour it into a mold, dry it, and sinter it at 650 °C to prepare porous tourmaline balls with a particle size of 0.1 mm; the mass fractions of each component of the low melting point powder are: ZnO: 15 parts; H3BO4: 15 parts; SiO2: 30 parts; Al2O3: 10 parts; K2CO3: 10 parts; Na2CO3: 10 parts;

[0028] (2) Add the porous tourmaline balls to the ball mill tank, add 4-hydroxycrotonic acid and zirconia balls, control the ball mill speed at 300 r / min and the ball-to-material ratio at 15:1. First, ball mill for 0.5 h, then add di-tert-butyl peroxide to the tank, and continue to ball mill for 0.5 h under the protection of inert gas. Take out 1 / 2 to obtain the first modified tourmaline, and grind the remaining 1 / 2 to a particle size of 300 nm, and freeze-dry at -30 °C for 6 h to obtain modified tourmaline nanopowder; the mass ratio of tourmaline powder, 4-hydroxycrotonic acid, and di-tert-butyl peroxide is 100:20:5;

[0029] (3) Add 4 parts by mass of agarwood fibers to an aqueous solution of sodium periodate with a concentration of 0.075 mol / L, with a ratio of 4 g:200 mL. Then add isopropanol until the volume fraction of isopropanol is 6.3%. React at 30 °C for 6 h respectively, cover the container with aluminum foil, and react in the dark. After the reaction is completed, add an equal volume of 0.1 mol / L ethylene glycol aqueous solution of isopropanol and continue to react for 0.5 h. Then wash 3 times with distilled water and absolute ethanol respectively and drain, and freeze-dry at -18 °C for 12 h to obtain aldehyde group agarwood fibers;

[0030] (4) After freeze-drying 0.8 parts by mass of the first modified tourmaline at -30 °C for 6 h, add 0.1 parts by mass of lemon peel powder with a particle size of 10 nm, control the ball mill speed at 500 r / min and the ball-to-material ratio at 20:1, and ball mill for 20 min to obtain the second modified tourmaline;

[0031] (5) Disperse the secondarily modified tourmaline in soft water. Under ultrasonic waves of 20 kHz, add aldehyde-group-containing aloeswood fibers to obtain a dispersion with a solid content of 50 wt%. The mass ratio of the aldehyde-group-containing aloeswood fibers to the secondarily modified tourmaline is 5:1. Add a silver ammonia solution with a volume 0.25 times that of the soft water. Heat and react in a water bath at 90 °C for 1 h, drain, and freeze-dry at -18 °C for 12 h to obtain modified aloeswood fibers;

[0032] (6) Mix 30 parts by mass of the regenerated cellulose spinning dope, 10 parts by mass of the modified tourmaline nanopowder, and 30 parts by mass of the ordinary spinning sizing solution. After stirring at 500 rpm for 10 min, add 10 parts by mass of the modified aloeswood fibers, and perform degassing and spinning to obtain regenerated cellulose fibers containing aloeswood.

[0033] Example 2

[0034] (1) Mix 100 parts by mass of 2-μm tourmaline and 20 parts by mass of 2-μm low-melting-point powder to form a mixture. Then, mix dextrin and water at 80 °C in a mass ratio of 1:9 to form a mixed solution. Add the mixed solution to the mixture. The mass ratio of tourmaline to dextrin is 85:9. Mix and stir until it becomes a muddy state, pour it into a mold, dry it, and sinter it at 700 °C to prepare porous tourmaline balls with a particle size of 0.6 mm; The mass fractions of the components of the low-melting-point powder are as follows: ZnO: 17 parts; H3BO4: 17 parts; SiO2: 35 parts; Al2O3: 11 parts; K2CO3: 12 parts; Na2CO3: 11 parts;

[0035] (2) Add the porous tourmaline balls to the ball mill tank body, add 4-hydroxycrotonic acid and zirconia balls. Control the ball milling speed at 400 r / min and the ball-to-material ratio at 15:1. First, ball mill for 1 h, then add di-tert-butyl peroxide to the tank body, and continue ball milling for 0.5 h under inert gas protection. Take out 1 / 2 to obtain the first modified tourmaline, and continue grinding the remaining 1 / 2 until the particle size reaches 400 nm. Freeze-dry at -30 °C for 6 h to obtain modified tourmaline nanopowder; The mass ratio of tourmaline powder, 4-hydroxycrotonic acid, and di-tert-butyl peroxide is 100:30:7;

[0036] (3) Add 4 parts by mass of aloeswood fibers to an aqueous solution of sodium periodate with a concentration of 0.075 mol / L, with a ratio of 4 g:200 mL. Then add isopropanol until the volume fraction of isopropanol reaches 6.3%. React at 30 °C for 6 h respectively. Cover the container with aluminum foil and react in the dark. After the reaction is completed, add an aqueous solution of ethylene glycol with a concentration of 0.1 mol / L with the same volume as that of isopropanol and continue to react for 0.5 h. Then wash 3 times with distilled water and absolute ethanol respectively and drain, and freeze-dry at -18 °C for 12 h to obtain aldehyde-group-containing aloeswood fibers;

[0037] (4) After freeze-drying 1.0 part by mass of the first modified tourmaline at -30°C for 6 h, 0.3 part by mass of lemon peel powder with a particle size of 15 nm was added, the rotation speed of ball milling was controlled at 500 r / min, the ball-to-material ratio was 20:1, and ball milling was carried out for 30 min to obtain the second modified tourmaline;

[0038] (5) The second modified tourmaline was dispersed in soft water, and aldehyde-grouped agarwood fibers were added under 20 kHz ultrasound to obtain a dispersion with a solid content of 50 wt%. The mass ratio of aldehyde-grouped agarwood fibers to the second modified tourmaline was 5:1. A silver ammonia solution 0.25 times the volume of the added soft water was added, and the reaction was carried out by water bath heating at 90°C for 2 h, then dried by suction and freeze-dried at -18°C for 12 h to obtain modified agarwood fibers;

[0039] (6) 40 parts by mass of regenerated cellulose spinning dope, 15 parts by mass of modified tourmaline nanopowder, and 50 parts by mass of ordinary spinning sizing solution were mixed, stirred at 500 rpm for 10 min, then 20 parts by mass of modified agarwood fibers were added, and after degassing and spinning, regenerated cellulose fibers containing agarwood were obtained.

[0040] Example 3

[0041] (1) 100 parts by mass of 3-μm tourmaline and 30 parts by mass of 1-μm low-melting-point powder were mixed to form a mixture. Then, dextrin and water at 80°C were mixed in a mass ratio of 1:10 to form a mixed solution. The mixed solution was added to the mixture, and the mass ratio of tourmaline to dextrin was 85:9. After mixing and stirring until it became a muddy state, it was poured into a mold, dried and then sintered at 750°C to prepare porous tourmaline balls with a particle size of 1 mm; the mass fractions of each component of the low-melting-point powder were: ZnO: 18 parts; H3BO4: 15 parts; SiO2: 32 parts; Al2O3: 11 parts; K2CO3: 12 parts; Na2CO3: 10 parts;

[0042] (2) The porous tourmaline balls were added to the ball milling tank body, 4-hydroxycrotonic acid and zirconia balls were added, the rotation speed of ball milling was controlled at 500 r / min, the ball-to-material ratio was 15:1, ball milling was carried out for 2 h first, then di-tert-butyl peroxide was added to the tank body, and ball milling was continued for 0.6 h under inert gas protection. 1 / 2 was taken out to obtain the first modified tourmaline, and the remaining 1 / 2 was continuously ground to a particle size of 500 nm and freeze-dried at -30°C for 6 h to obtain modified tourmaline nanopowder; the mass ratio of tourmaline powder, 4-hydroxycrotonic acid and di-tert-butyl peroxide was 100:30:5;

[0043] (3) Add 4 parts by mass of agarwood fibers to an aqueous solution of sodium periodate at 0.075 mol / L, with a ratio of 4 g: 200 mL. Then add isopropanol until the volume fraction of isopropanol is 6.3%. React at 30 °C for 6 h respectively. Cover the container with aluminum foil and react in the dark. After the reaction is completed, add an equal volume of 0.1 mol / L ethylene glycol aqueous solution of isopropanol and continue to react for 0.5 h. Then wash 3 times with distilled water and absolute ethanol respectively and drain. Freeze-dry at -18 °C for 12 h to obtain aldehyde-group agarwood fibers;

[0044] (4) After freeze-drying 1.2 parts by mass of the first modified tourmaline at -30 °C for 6 h, add 0.3 part by mass of pericarp powder with a particle size of 10 - 20 nm. Control the rotation speed of ball milling at 500 r / min and the ball-to-material ratio at 20:1. Ball mill for 40 min to obtain the second modified tourmaline; the pericarp powder is prepared by drying and pulverizing lemon peel or citrus peel;

[0045] (5) Disperse the second modified tourmaline in soft water. Under ultrasonic wave at 20 kHz, add aldehyde-group agarwood fibers to obtain a dispersion with a solid content of 50 wt%. The mass ratio of aldehyde-group agarwood fibers to the second modified tourmaline is 5:1. Add a silver ammonia solution with a volume 0.25 times that of soft water. Heat and react in a water bath at 90 °C for 2 h. Drain and freeze-dry at -18 °C for 12 h to obtain modified agarwood fibers;

[0046] (6) Mix 50 parts by mass of regenerated cellulose spinning dope, 20 parts by mass of modified tourmaline nanopowder, and 30 parts by mass of ordinary spinning sizing solution. Stir at 500 rpm for 10 min, then add 10 parts by mass of modified agarwood fibers. After defoaming and spinning, regenerated cellulose fibers containing agarwood are obtained.

[0047] Comparative Example 1 (using ordinary tourmaline instead of porous tourmaline balls)

[0048] (1) Add 0.6 mm tourmaline to the ball milling tank body, add 4-hydroxycrotonic acid and zirconia balls. Control the rotation speed of ball milling at 400 r / min and the ball-to-material ratio at 15:1. First ball mill for 1 h, then add di-tert-butyl peroxide to the tank body and continue to ball mill for 0.5 h under inert gas protection. Take out 1 / 2 to obtain the first modified tourmaline, and continue to grind the remaining 1 / 2 until the particle size is 400 nm. Freeze-dry at -30 °C for 6 h to obtain modified tourmaline nanopowder; the mass ratio of tourmaline powder, 4-hydroxycrotonic acid, and di-tert-butyl peroxide is 100:30:7;

[0049] (2) Add 4 parts by mass of agarwood fiber to an aqueous solution of sodium periodate at 0.075 mol / L, with a ratio of 4 g: 200 mL. Then add isopropanol until the volume fraction of isopropanol is 6.3%. React at 30 °C for 6 h respectively. Cover the container with aluminum foil and react in the dark. After the reaction is completed, add an equal volume of 0.1 mol / L ethylene glycol aqueous solution of isopropanol and continue to react for 0.5 h. Then wash 3 times with distilled water and absolute ethanol respectively and drain. Freeze-dry at -18 °C for 12 h to obtain aldehyde-group-containing agarwood fiber;

[0050] (3) After freeze-drying 1.0 part by mass of the first-modified tourmaline at -30 °C for 6 h, add 0.3 part by mass of lemon peel powder with a particle size of 15 nm. Control the rotation speed of ball milling at 500 r / min and the ball-to-material ratio at 20:1, and ball mill for 30 min to obtain a composite powder;

[0051] (4) Disperse the composite powder in soft water. Under ultrasonic waves at 20 kHz, add aldehyde-group-containing agarwood fiber to obtain a dispersion with a solid content of 50 wt%. The mass ratio of aldehyde-group-containing agarwood fiber to the composite powder is 5:1. Add a silver ammonia solution with a volume 0.25 times that of soft water, and react in a water bath at 90 °C for 2 h. Drain, and freeze-dry at -18 °C for 12 h to obtain modified agarwood fiber;

[0052] (5) Mix 40 parts by mass of regenerated cellulose spinning dope, 15 parts by mass of modified tourmaline nanof powder, and 50 parts by mass of ordinary spinning sizing solution. After stirring at 500 rpm for 10 min, add 20 parts by mass of modified agarwood fiber, and obtain regenerated cellulose fiber containing agarwood through degassing and spinning.

[0053] Comparative Example 2 (without adding 4-hydroxycrotonic acid)

[0054] (1) Mix 100 parts by mass of 2-μm tourmaline and 20 parts by mass of 2-μm low-melting-point powder to form a mixture. Then mix dextrin and water at 80 °C in a mass ratio of 1:9 to form a mixed solution. Add the mixed solution to the mixture. The mass ratio of tourmaline to dextrin is 85:9. Mix and stir until it becomes a muddy state, pour it into a mold, dry it, and sinter at 700 °C to prepare a porous tourmaline ball with a particle size of 0.6 mm; The mass fractions of each component of the low-melting-point powder are as follows: ZnO: 17 parts; H3BO4: 17 parts; SiO2: 35 parts; Al2O3: 11 parts; K2CO3: 12 parts; Na2CO3: 11 parts;

[0055] (2) Add the porous tourmaline ball to the ball milling tank body, add zirconia balls, control the rotation speed of ball milling at 400 r / min and the ball-to-material ratio at 15:1. First ball mill for 1 h, take out 1 / 2 to obtain the first-modified tourmaline, and continue to grind the remaining 1 / 2 until the particle size is 400 nm. Freeze-dry at -30 °C for 6 h to obtain modified tourmaline nanof powder;

[0056] (3) Add 4 parts by mass of agarwood fibers to an aqueous solution of sodium periodate at 0.075 mol / L, with a ratio of 4 g:200 mL. Then add isopropanol until the volume fraction of isopropanol is 6.3%. React at 30 °C for 6 h respectively. Cover the container with aluminum foil and react in the dark. After the reaction is completed, add an aqueous solution of ethylene glycol at 0.1 mol / L with the same volume as isopropanol and continue to react for 0.5 h. Then wash 3 times with distilled water and absolute ethanol respectively and drain. Freeze-dry at -18 °C for 12 h to obtain aldehyde-group-containing agarwood fibers;

[0057] (4) After freeze-drying 1.0 part by mass of the first modified tourmaline at -30 °C for 6 h, add 0.3 part by mass of lemon peel powder with a particle size of 15 nm. Control the rotation speed of ball milling to be 500 r / min and the ball-to-material ratio to be 20:1, and ball mill for 30 min to obtain a composite powder;

[0058] (5) Disperse the composite powder in soft water. Under ultrasonic wave at 20 kHz, add aldehyde-group-containing agarwood fibers to obtain a dispersion with a solid content of 50 wt%. The mass ratio of aldehyde-group-containing agarwood fibers to the composite powder is 5:1. Add a silver ammonia solution with 0.25 times the volume of soft water, and react in a water bath at 90 °C for 2 h. Drain, and freeze-dry at -18 °C for 12 h to obtain modified agarwood fibers;

[0059] (6) Mix 40 parts by mass of regenerated cellulose spinning dope, 15 parts by mass of modified tourmaline nanopowder, and 50 parts by mass of ordinary spinning sizing solution. After stirring at 500 rpm for 10 min, add 20 parts by mass of modified agarwood fibers, and obtain regenerated cellulose fibers containing agarwood through degassing and spinning.

[0060] Comparative Example 3 (Tourmaline is not ground in batches)

[0061] (1) Mix 100 parts by mass of 2-μm tourmaline and 20 parts by mass of 2-μm low-melting-point powder to form a mixture. Then mix dextrin and water at 80 °C according to a mass ratio of 1:9 to form a mixed solution. Add the mixed solution to the mixture, with the mass ratio of tourmaline to dextrin being 85:9. Mix and stir until it becomes a muddy state, pour it into a mold, dry it, and sinter at 700 °C to prepare porous tourmaline balls with a particle size of 0.6 mm; The mass fractions of each component of the low-melting-point powder are: ZnO: 17 parts; H3BO4: 17 parts; SiO2: 35 parts; Al2O3: 11 parts; K2CO3: 12 parts; Na2CO3: 11 parts;

[0062] (2) Add the porous tourmaline balls into the ball milling tank body, add 4-hydroxycrotonic acid and zirconia balls, control the rotation speed of ball milling at 400 r / min and the ball-to-material ratio at 15:1, first ball mill for 1 h, then add di-tert-butyl peroxide into the tank body, and continue ball milling under the protection of inert gas until the particle size reaches 400 nm, and freeze-dry at -30 °C for 6 h to obtain modified tourmaline nanoflour; the mass ratio of tourmaline powder, 4-hydroxycrotonic acid and di-tert-butyl peroxide is 100:30:7;

[0063] (3) Add 4 parts by mass of agarwood fibers into an aqueous solution of sodium periodate with a concentration of 0.075 mol / L, with a ratio of 4 g:200 mL, then add isopropanol until the volume fraction of isopropanol is 6.3%, react at 30 °C for 6 h respectively, cover the container with aluminum foil and react in the dark. After the reaction is completed, add an aqueous solution of ethylene glycol with a concentration of 0.1 mol / L with the same volume as isopropanol and continue to react for 0.5 h, then wash 3 times with distilled water and absolute ethanol respectively and drain, and freeze-dry at -18 °C for 12 h to obtain aldehyde-group agarwood fibers;

[0064] (4) Mix 1.0 part by mass of the modified tourmaline nanoflour and 0.3 part by mass of lemon peel powder with a particle size of 15 nm, control the rotation speed of ball milling at 500 r / min and the ball-to-material ratio at 20:1, and ball mill for 30 min to obtain secondary modified tourmaline;

[0065] (5) Disperse the secondary modified tourmaline in soft water, add aldehyde-group agarwood fibers under ultrasonic wave at 20 kHz to obtain a dispersion with a solid content of 50 wt%, the mass ratio of aldehyde-group agarwood fibers to secondary modified tourmaline is 5:1, add a silver ammonia solution with a volume 0.25 times that of the soft water, heat and react in a water bath at 90 °C for 2 h, drain, and freeze-dry at -18 °C for 12 h to obtain modified agarwood fibers;

[0066] (6) Mix 40 parts by mass of regenerated cellulose spinning dope, 50 parts by mass of ordinary spinning sizing solution, and 20 parts by mass of modified agarwood fibers, and obtain regenerated cellulose fibers containing agarwood through degassing and spinning.

[0067] Comparative Example 4 (Tourmaline is not ground in batches)

[0068] (1) Mix 100 parts by mass of 2-μm tourmaline and 20 parts by mass of 2-μm low melting point powder to form a mixture, then mix dextrin and water at 80 °C in a mass ratio of 1:9 to form a mixed solution, add the mixed solution to the mixture, the mass ratio of tourmaline to dextrin is 85:9, mix and stir until it becomes a muddy state, pour it into a mold, dry it, and sinter at 700 °C to prepare porous tourmaline balls with a particle size of 0.6 mm; the mass fractions of each component of the low melting point powder are: ZnO: 17 parts; H3BO4: 17 parts; SiO2: 35 parts; Al2O3: 11 parts; K2CO3: 12 parts; Na2CO3: 11 parts;

[0069] (2) Add the porous tourmaline balls into the ball mill tank body, add 4-hydroxycrotonic acid and zirconia balls, control the rotation speed of the ball mill at 400 r / min and the ball-to-material ratio at 15:1, first ball mill for 1 h, then add di-tert-butyl peroxide into the tank body, and continue to ball mill for 0.5 h under the protection of inert gas to obtain modified tourmaline nanoflour; the mass ratio of tourmaline powder, 4-hydroxycrotonic acid and di-tert-butyl peroxide is 100:30:7;

[0070] (3) Add 4 parts by mass of agarwood fiber into an aqueous solution of sodium periodate with a concentration of 0.075 mol / L, with a ratio of 4 g:200 mL, then add isopropanol until the volume fraction of isopropanol is 6.3%, react at 30 °C for 6 h respectively, cover the container with aluminum foil and react in the dark. After the reaction is completed, add an aqueous solution of ethylene glycol with a concentration of 0.1 mol / L with the same volume as isopropanol and continue to react for 0.5 h, then wash 3 times with distilled water and absolute ethanol respectively and drain, and freeze-dry at -18 °C for 12 h to obtain aldehyde-group agarwood fiber;

[0071] (4) Disperse the aldehyde-group agarwood fiber in soft water to obtain a dispersion with a solid content of 50 wt%, add a silver ammonia solution with a volume 0.25 times that of the soft water, heat and react in a water bath at 90 °C for 2 h, drain, and freeze-dry at -18 °C for 12 h to obtain modified agarwood fiber;

[0072] (5) Mix 40 parts by mass of regenerated cellulose spinning dope, 15 parts by mass of modified tourmaline nanoflour, 5 parts of lemon peel powder with a particle size of 15 nm, and 50 parts by mass of ordinary spinning sizing solution. After stirring at 500 rpm for 10 min, add 20 parts by mass of modified agarwood fiber, and obtain regenerated cellulose fiber containing agarwood through defoaming and spinning.

[0073] Comparative Example 5 (Do not perform secondary grinding modification on the first modified tourmaline)

[0074] (1) Mix 100 parts by mass of 2-μm tourmaline and 20 parts by mass of 2-μm low melting point powder to form a mixture, then mix dextrin and water at 80 °C in a mass ratio of 1:9 to form a mixed solution, add the mixed solution to the mixture, and the mass ratio of tourmaline to dextrin is 85:9. Mix and stir until it becomes a muddy state, pour it into a mold, dry it, and sinter at 700 °C to prepare porous tourmaline balls with a particle size of 0.6 mm; the mass fractions of each component of the low melting point powder are: ZnO: 17 parts; H3BO4: 17 parts; SiO2: 35 parts; Al2O3: 11 parts; K2CO3: 12 parts; Na2CO3: 11 parts;

[0075] (2) Add the porous tourmaline balls into the ball milling tank, add 4-hydroxycrotonic acid and zirconia balls, control the rotation speed of ball milling at 400 r / min and the ball-to-material ratio at 15:1. First, ball mill for 1 h, then add di-tert-butyl peroxide into the tank, and continue to ball mill for 0.5 h under the protection of inert gas. Take out 1 / 2 to obtain the first modified tourmaline, and grind the remaining 1 / 2 until the particle size reaches 400 nm, and freeze-dry at -30 °C for 6 h to obtain the modified tourmaline nanopowder; the mass ratio of tourmaline powder, 4-hydroxycrotonic acid and di-tert-butyl peroxide is 100:30:7;

[0076] (3) Add 4 parts by mass of agarwood fibers into an aqueous solution of sodium periodate at 0.075 mol / L, with a ratio of 4 g:200 mL. Then add isopropanol until the volume fraction of isopropanol is 6.3%. React at 30 °C for 6 h respectively. Cover the container with aluminum foil and react in the dark. After the reaction is completed, add an aqueous solution of ethylene glycol at 0.1 mol / L with the same volume as isopropanol and continue to react for 0.5 h. Then wash 3 times with distilled water and absolute ethanol respectively and drain. Freeze-dry at -18 °C for 12 h to obtain aldehyde-group agarwood fibers;

[0077] (4) Disperse the first modified tourmaline and lemon peel powder with a particle size of 15 nm in soft water. Under ultrasonic wave at 20 kHz, add aldehyde-group agarwood fibers to obtain a dispersion with a solid content of 50 wt%. The mass ratio of aldehyde-group agarwood fibers to the second modified tourmaline is 5:1:0.3. Add a silver ammonia solution with a volume 0.25 times that of soft water, and react in a water bath at 90 °C for 2 h. Drain, and freeze-dry at -18 °C for 12 h to obtain modified agarwood fibers;

[0078] (5) Mix 40 parts by mass of regenerated cellulose spinning dope, 15 parts by mass of modified tourmaline nanopowder, and 50 parts by mass of ordinary spinning sizing solution. After stirring at 500 rpm for 10 min, add 20 parts by mass of modified agarwood fibers, and obtain regenerated cellulose fibers containing agarwood through degassing and spinning.

[0079] Comparative Example 6 (The second modified tourmaline is not preferentially mixed with aldehyde-group agarwood fibers)

[0080] (1) Mix 100 parts by mass of 2-μm tourmaline and 20 parts by mass of 2-μm low melting point powder to form a mixture. Then mix dextrin and water at 80 °C according to a mass ratio of 1:9 to form a mixed solution. Add the mixed solution to the mixture. The mass ratio of tourmaline to dextrin is 85:9. Mix and stir until it becomes a muddy state, pour it into a mold, dry it, and sinter at 700 °C to prepare porous tourmaline balls with a particle size of 0.6 mm; the mass fractions of each component of the low melting point powder are: ZnO: 17 parts; H3BO4: 17 parts; SiO2: 35 parts; Al2O3: 11 parts; K2CO3: 12 parts; Na2CO3: 11 parts;

[0081] (2) Add porous tourmaline balls into the ball mill tank, add 4-hydroxycrotonic acid and zirconia balls, control the rotation speed of ball milling at 400 r / min and the ball-to-material ratio at 15:1. First, ball mill for 1 h, then add di-tert-butyl peroxide into the tank, and continue ball milling for 0.5 h under the protection of inert gas. Take out 1 / 2 to obtain the first modified tourmaline, and grind the remaining 1 / 2 until the particle size reaches 400 nm, and freeze-dry at -30 °C for 6 h to obtain modified tourmaline nanopowder; the mass ratio of tourmaline powder, 4-hydroxycrotonic acid and di-tert-butyl peroxide is 100:30:7;

[0082] (3) Add 4 parts by mass of agarwood fibers into an aqueous solution of sodium periodate with a concentration of 0.075 mol / L, with a ratio of 4 g:200 mL. Then add isopropanol until the volume fraction of isopropanol reaches 6.3%. React at 30 °C for 6 h respectively. Cover the container with aluminum foil and react in the dark. After the reaction is completed, add an equal volume of 0.1 mol / L ethylene glycol aqueous solution of isopropanol and continue to react for 0.5 h. Then wash 3 times with distilled water and absolute ethanol respectively and drain, and freeze-dry at -18 °C for 12 h to obtain aldehyde-group agarwood fibers;

[0083] (4) After freeze-drying 1.0 part by mass of the first modified tourmaline at -30 °C for 6 h, add 0.3 part by mass of lemon peel powder with a particle size of 15 nm, control the rotation speed of ball milling at 500 r / min and the ball-to-material ratio at 20:1, and ball mill for 30 min to obtain the second modified tourmaline;

[0084] (5) Disperse aldehyde-group agarwood fibers in soft water to obtain a dispersion with a solid content of 50 wt%. Add a silver ammonia solution with a volume 0.25 times that of the soft water, and react in a water bath at 90 °C for 2 h. Drain, and freeze-dry at -18 °C for 12 h to obtain modified agarwood fibers;

[0085] (6) Mix 40 parts by mass of regenerated cellulose spinning dope, 15 parts by mass of modified tourmaline nanopowder, and 50 parts by mass of ordinary spinning sizing solution. After stirring at 500 rpm for 10 min, add 20 parts by mass of modified agarwood fibers and 10 parts by mass of the second modified tourmaline, and obtain regenerated cellulose fibers containing agarwood through defoaming and spinning.

[0086] Performance Test

[0087] (I) Aroma Stability Test

[0088] Aroma stability detection method: Wash the sample 100 times and place it for 365 days under natural conditions.

[0089] Evaluation method: A review panel composed of perfume experts qualitatively determines the aroma by smell.

[0090] (II) Deodorization Performance Test

[0091] Detection method: Place the regenerated cellulose fiber cloth in a sealed container with a known odor concentration C0. The odor components are a mixed gas composed of ammonia and hydrogen sulfide gas. Seal and place it for 60 minutes, then use a detection instrument to measure the odor concentration C1 in the sealed instrument, and calculate the odor removal rate of the sample according to the following formula. The test results are shown in Table 1.

[0092] Calculation formula: Odor removal rate (%) = (C0 - C1) / C0 × 100%, where C0 is the initial odor concentration and C1 is the residual odor concentration adsorbed by the fiber product.

[0093] The following Table 1 shows the performance analysis results of xxxxx using Examples 1 to 3 and Comparative Examples 1 to xx of the present invention.

[0094] Table 1

[0095]

[0096]

[0097] The present invention uses modified agarwood fibers to reinforce the regenerated cellulose matrix to obtain high-strength and high-toughness fibers. The modified agarwood fibers are modified by silver ions and aldehyde groups. When mixed with secondary-modified tourmaline, the fruit peel powder helps to reduce silver ions, so that the fiber surface is loaded with nano-silver, and good antibacterial properties are exhibited under the combined action. The present invention uses large-particle-size porous tourmaline, combined with 4-hydroxycrotonic acid for grinding modification, so that it combines with regenerated cellulose to enhance the fiber strength. Through the secondary grinding modification of nano-level fruit peel powder, the pores of tourmaline are filled, the activity of fruit peel powder is improved, and it is loaded inside the tourmaline. The modified tourmaline is mixed with agarwood fibers, combined by chemical bonds, and the fibers are curled to wrap the fruit peel powder by ultrasonic action, reducing the spinning and washing losses, and improving the long-lasting fragrance and deodorizing effect of the fibers.

[0098] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-mentioned exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, in any regard, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claimed rights.

Claims

1. A preparation method of a regenerated cellulose fiber containing agarwood, characterized in that, It includes the following preparation steps: (1) Add porous tourmaline balls with a particle size of 0.1 - 1 mm into the ball mill tank, add 4 - hydroxycrotonic acid, first ball mill for 0.5 - 2 h, then add an initiator into the tank, and continue to ball mill for 0.5 - 0.6 h under the protection of inert gas. Take out 1 / 2 to obtain the first modified tourmaline, and grind the remaining 1 / 2 until the particle size is 300 - 500 nm, and freeze - dry at - 30 °C for 6 h to obtain modified tourmaline nanopowder; (2) After freeze - drying 0.8 - 1.2 parts by mass of the first modified tourmaline at - 30 °C for 6 h, add 0.1 - 0.6 parts by mass of peel powder with a particle size of 10 - 20 nm, and ball mill for 20 - 40 min to obtain the second modified tourmaline; (3) Disperse the second modified tourmaline in soft water, under 20 kHz ultrasonic wave, add aldehyde - group agarwood fibers to obtain a dispersion with a solid content of 50 wt%, add a silver ammonia solution with a volume 0.25 times that of the soft water, heat and react in a water bath at 90 °C for 0 - 2 h, drain, and freeze - dry at - 18 °C for 12 h to obtain modified agarwood fibers; (4) Mix 30 - 50 parts by mass of regenerated cellulose spinning dope, 10 - 20 parts by mass of modified tourmaline nanopowder, and 30 - 50 parts by mass of ordinary spinning sizing solution, stir at 500 rpm for 10 min, then add 10 - 20 parts by mass of modified agarwood fibers, and obtain regenerated cellulose fibers containing agarwood through degassing and spinning.

2. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that, The pore diameter of the porous tourmaline ball described in step (1) is between 2 and 50 nm, and the specific surface area is above 600 m 2 / g.

3. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that, During the ball - milling process in step (1), control the ball - milling speed at 300 - 500 r / min and the ball - to - material ratio at 15:

1.

4. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that, The initiator in step (1) is di - tert - butyl peroxide.

5. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that The peel powder in step (2) is prepared by drying and pulverizing lemon peel or citrus peel.

6. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, wherein, The particle size of the peel powder in step (2) is 10 - 20 nm.

7. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that, During the ball - milling process in step (2), control the ball - milling speed at 500 r / min and the ball - to - material ratio at 20:

1.

8. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that, The aldehyde - group agarwood fibers in step (3) are prepared by oxidizing agarwood fibers with sodium periodate.

9. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that, The mass ratio of the aldehyde - group agarwood fibers to the second modified tourmaline in step (3) is 5:

1.

10. The preparation method of a regenerated cellulose fiber containing agarwood according to claim 1, characterized in that, The ordinary spinning sizing solution in step (4) has a methylcellulose content of 9.4%, a viscosity of 42 S, and an alkali content of 5.3%.

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