阅读说明：本技术 一种含有植物精油的莱赛尔纤维及其制备方法 (Lyocell fiber containing plant essential oil and preparation method thereof ) 是由 姚勇波 颜志勇 许志 李喆 生俊露 易洪雷 李海东 于 2021-05-08 设计创作，主要内容包括：本发明涉及一种含有植物精油的莱赛尔纤维及其制备方法,制备方法为：首先将植物精油和纳米无机粉体(经过疏水改性处理)均匀混合制成植物精油/纳米无机粉体混合物,然后采用螺杆挤出机将其与功能母液基液(包含纤维素和醋酸纤维素)混合制成植物精油功能母液,最后将植物精油功能母液与莱赛尔纺丝溶液混合(二者粘度差不超过1000Pa·s)后纺丝制得含有植物精油的莱赛尔纤维；最终制得的纤维主要由莱赛尔纤维主体、纳米无机粉体和植物精油组成；植物精油附着在纳米无机粉体上,纳米无机粉体分散在莱赛尔纤维主体中,莱赛尔纤维主体由纤维素和醋酸纤维素组成。本发明成形过程植物精油流失量少,能够有效减缓植物精油的释放。(The invention relates to a lyocell fiber containing plant essential oil and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, uniformly mixing plant essential oil and nano inorganic powder (subjected to hydrophobic modification treatment) to prepare a plant essential oil/nano inorganic powder mixture, then mixing the plant essential oil/nano inorganic powder mixture with a functional mother liquor base solution (containing cellulose and cellulose acetate) by adopting a screw extruder to prepare a plant essential oil functional mother liquor, and finally mixing the plant essential oil functional mother liquor with a lyocell spinning solution (the viscosity difference between the plant essential oil functional mother liquor and the lyocell spinning solution is not more than 1000 Pa.s) and spinning to prepare lyocell fibers containing the plant essential oil; the finally prepared fiber mainly comprises a lyocell fiber main body, nano inorganic powder and plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate. The forming process of the invention has less loss of the plant essential oil and can effectively slow down the release of the plant essential oil.)

1. A preparation method of lyocell fiber containing plant essential oil is characterized in that the plant essential oil and nano inorganic powder are uniformly mixed to prepare a plant essential oil/nano inorganic powder mixture, then the plant essential oil/nano inorganic powder mixture is mixed with a functional mother liquor base solution by adopting a screw extruder to prepare a plant essential oil functional mother liquor, finally the plant essential oil functional mother liquor and a lyocell spinning solution are mixed to prepare a lyocell spinning solution containing the plant essential oil, and then the lyocell fiber containing the plant essential oil is obtained by spinning;

carrying out hydrophobic modification treatment on the nano inorganic powder;

the functional mother solution base solution comprises cellulose and cellulose acetate;

the plant essential oil functional mother liquor and the lyocell spinning solution meet the following requirements: 0< B-A is less than or equal to 1000 Pa.s, wherein A is the viscosity of the plant essential oil functional mother liquor, and B is the viscosity of the lyocell spinning solution.

2. The method for preparing a lyocell fiber containing vegetable essential oils according to claim 1, wherein the vegetable essential oils are composed of a single essential oil and a base oil;

the nano inorganic powder is more than one of nano titanium dioxide, nano silicon dioxide and carbon black; the specific surface area of the nano inorganic powder is 30-250 m²/g；

In the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 10-25%.

3. The method for preparing a lyocell fiber containing vegetable essential oil according to claim 2, wherein the single essential oil is lavender oil, rosemary oil, lemon oil, clove oil, peppermint oil, cinnamon oil, or thyme oil; the base oil is oleum Armeniacae amarum, oleum Simmondsia chinensis, grapeseed oil, and wheat germ oil.

4. The method for preparing lyocell fiber containing vegetable essential oil according to claim 1, wherein the functional mother liquor base solution is composed of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 600-900, and the esterification degree of the cellulose acetate is 1-2;

in the functional mother liquor base solution, the mass fraction of cellulose is 6-10%, the mass fraction of cellulose acetate is 1-2%, and the mass fraction of NMMO is 75-77%;

the mass ratio of the functional mother liquor base solution to the plant essential oil/nano inorganic powder mixture is 1-3: 1;

the temperature for mixing the plant essential oil/nano inorganic powder mixture and the functional mother solution base liquid is 90-100 ℃, and the time is 5-10 min.

5. The method for preparing lyocell fiber containing vegetable essential oil according to claim 1, wherein the lyocell spinning solution is composed of cellulose, NMMO and water; the polymerization degree of the cellulose is 400-600;

in the lyocell spinning solution, the mass fraction of cellulose is 8-15%, and the mass fraction of NMMO is 75-77%;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 1-3;

the viscosity of the plant essential oil functional mother liquor is 9000-14000 Pa.s, and the viscosity of the lyocell spinning solution is 9500-15000 Pa.s.

6. The method for preparing lyocell fiber containing vegetable essential oil according to claim 1, wherein the spinning process comprises: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 10-25%, and the temperature of the coagulating bath is 15-25 ℃.

7. The method for preparing the lyocell fiber containing the vegetable essential oil according to claim 1, wherein the fiber is further post-finished with an organic silicon finishing agent after spinning;

the organic silicon finishing agent consists of 2-4 wt% of methyl hydrogen-containing silane emulsion, 5-8 wt% of hydroxyl silane emulsion, 1-2 wt% of aminated epoxy cross-linking agent, 0.8-1.2 wt% of crystalline zinc acetate, 0.4-0.8 wt% of zirconium oxychloride, 0.3-0.6 wt% of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: dipping → drying → baking → washing with water → oiling → drying;

the liquid carrying rate is controlled to be 60-80% during dipping, the first drying temperature is 100-105 ℃, the baking temperature is 120-140 ℃, and the baking time is 3-5 min.

8. The plant essential oil-containing lyocell fiber prepared by the method for preparing a plant essential oil-containing lyocell fiber according to any one of claims 1 to 7, which is characterized by mainly comprising a lyocell fiber main body, nano inorganic powder and plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate.

9. The vegetable essential oil-containing lyocell fiber according to claim 8, wherein the vegetable essential oil-containing lyocell fiber has a fineness of 1.2 to 3.5dtex, a dry breaking strength of 2.0 to 4.5cN/dtex, a dry elongation at break of 11 to 20%, a wet breaking strength of 1.9 to 4.0cN/dtex, and a saturated moisture regain of 5 to 13%.

10. The lyocell fiber containing plant essential oil as claimed in claim 8, wherein the elution rate of the plant essential oil is 30-50% after the lyocell fiber containing plant essential oil is washed with water for 10 times according to the household washing and drying procedure for textile test GB/T8629-2017.

Technical Field

The invention belongs to the technical field of regenerated cellulose fibers, and relates to a lyocell fiber containing plant essential oil and a preparation method thereof.

Background

Lyocell (Lyocell) fiber is a regenerated cellulose fiber prepared by dry-jet wet spinning with an N-methylmorpholine-oxide (NMMO) aqueous solution as a solvent. The lyocell fiber has high strength, good moisture absorption performance, elegant luster and environment-friendly production process, and is a regenerated cellulose fiber variety with competitive advantages and development prospects. With the advancement of technology, functionally modified lyocell fibers are gradually emerging. Modified lyocell fibers available from austria lannerol include anti-fibril type (Lenzing lyocell a100, Lenzing lyocell LF), sunscreen-based anti-ultraviolet type (Lenzing lyocell sun/dull), and the like. Under the national institute of textile and plastics (TITK) of Tulin, GermanyThe brand develops skin-care functional Seacell and zinc oxide antibacterial Smartcel lyocell fibers containing algae additives. Cell of another brand under TITK flagThe microcapsule energy storage lyocell fiber and vitamin E skin-care lyocell fiber are possessed. The development history of the lyocell fiber in China is later than that of developed countries abroad, and the capacity expansion and quality improvement of the conventional lyocell fiberAt this stage, functional lyocell fibers are yet to be developed.

The plant essential oil is an aromatic substance extracted from plants and comprises various substances such as alcohols, aldehydes, acids, phenols, propiones, terpenes and the like. The plant essential oil has various types and functions, has various efficacies of regulating human metabolism, inhibiting bacteria and resisting bacteria, calming the nerves and restoring consciousness, repelling mosquitoes and expelling worms and the like, and is a high-grade skin-care and health-care product. The plant essential oil is combined with the cellulose fiber which is skin-friendly, so that the function can be better played. Plant essential oil is volatile and difficult to adhere to the surface of the fiber for a long time. Therefore, the plant essential oil is added into the cellulose solution by a spinning adding method and is spun and formed, so that the plant essential oil exists in the fiber, the loading capacity of the plant essential oil can be improved, and the release time can be prolonged.

In the prior art, a viscose fiber path is mainly adopted to prepare plant essential oil cellulose fibers, such as Chinese patent ZL201310140966.0 (viscose fibers with plant-derived antibacterial function and aromatic odor and a preparation method thereof), Chinese patent ZL201711470690.7 (regenerated cellulose fibers with antibacterial, anti-mite and mildew-proof functions and a preparation method thereof), and Chinese patent 201610946423.1 (functional plant aromatic, antibacterial cellulose fibers and a preparation method thereof), but the viscose fiber forming process is long and involves complex processes such as chemistry, physics and the like, the spinnability can be affected by directly adding essential oil, the essential oil loss rate is high, and the microcapsule method has the problems of large particle size, uneven distribution, blockage of a spinning nozzle, easy yarn breakage and the like. In addition, a trace amount of sulfur inevitably remains in the viscose fiber, and the fragrance of the plant essential oil is also adversely affected.

The lyocell fiber forming process is simple and only involves the physical process of solvent and non-solvent diffusion. However, the lyocell solvent NMMO is less chemically stable, is easily oxidized and is capable of reacting with Fe²⁺、Cu²⁺The metal ion reaction has strict requirements on the physical and chemical properties of the additive, and has practical significance if the lyocell fiber containing the plant essential oil can be prepared.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a lyocell fiber containing plant essential oil and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a method for preparing lyocell fiber containing plant essential oil, first mix plant essential oil, nanometer inorganic powder to make plant essential oil/nanometer inorganic powder mixture evenly, then use the screw extruder (it can provide strong shearing function) to mix it with mother solution base of function to make mother solution of function of plant essential oil, mix mother solution of function of plant essential oil and lyocell spinning solution to make lyocell spinning solution containing plant essential oil finally, the spinning gets lyocell fiber containing plant essential oil;

carrying out hydrophobic modification treatment on the nano inorganic powder;

the functional mother solution base solution comprises cellulose and cellulose acetate;

the plant essential oil functional mother liquor and the lyocell spinning solution meet the following requirements: 0< B-A is less than or equal to 1000 Pa.s, wherein A is the viscosity of the plant essential oil functional mother liquor, and B is the viscosity of the lyocell spinning solution.

As a preferred technical scheme:

the preparation method of the lyocell fiber containing the plant essential oil comprises the following steps of preparing the plant essential oil from the single component essential oil and the base oil;

the nano inorganic powder is more than one of nano titanium dioxide, nano silicon dioxide and carbon black; the specific surface area of the nano inorganic powder is 30-250 m²/g；

In the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 10-25%, and the rest components are the plant essential oil.

The preparation method of the lyocell fiber containing the plant essential oil comprises the following steps of preparing the single essential oil from lavender oil, rosemary oil, lemon oil, clove oil, peppermint oil, cinnamon oil or thyme oil; the base oil is sweet almond oil, jojoba oil, grape seed oil or wheat germ oil.

In the method for preparing the lyocell fiber containing the vegetable essential oil, the functional mother liquor base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 600-900, and the esterification degree of the cellulose acetate is 1-2;

in the functional mother liquor base solution, the mass fraction of cellulose is 6-10%, the mass fraction of cellulose acetate is 1-2%, and the mass fraction of NMMO is 75-77%;

the mass ratio of the functional mother liquor base solution to the plant essential oil/nano inorganic powder mixture is 1-3: 1;

the temperature for mixing the plant essential oil/nano inorganic powder mixture and the functional mother solution base liquid is 90-100 ℃, and the time is 5-10 min.

In the above method for preparing lyocell fiber containing vegetable essential oil, the lyocell spinning solution is composed of cellulose, NMMO and water; the polymerization degree of the cellulose is 400-600;

in the lyocell spinning solution, the mass fraction of cellulose is 8-15%, and the mass fraction of NMMO is 75-77%;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 1-3;

the viscosity of the plant essential oil functional mother liquor is 9000-14000 Pa.s, and the viscosity of the lyocell spinning solution is 9500-15000 Pa.s.

The preparation method of the lyocell fiber containing the vegetable essential oil comprises the following spinning processes: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 10-25%, and the temperature of the coagulating bath is 15-25 ℃.

According to the preparation method of the lyocell fiber containing the vegetable essential oil, after spinning is finished, the fiber is subjected to after-treatment by adopting the organic silicon finishing agent;

the organic silicon finishing agent consists of 2-4 wt% of methyl hydrogen-containing silane emulsion, 5-8 wt% of hydroxyl silane emulsion, 1-2 wt% of aminated epoxy cross-linking agent, 0.8-1.2 wt% of crystalline zinc acetate, 0.4-0.8 wt% of zirconium oxychloride, 0.3-0.6 wt% of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: dipping → drying → baking → washing with water → oiling → drying;

the liquid carrying rate is controlled to be 60-80% during dipping, the first drying temperature is 100-105 ℃, the baking temperature is 120-140 ℃, and the baking time is 3-5 min.

The invention also provides the lyocell fiber containing the plant essential oil prepared by the preparation method of the lyocell fiber containing the plant essential oil, which mainly comprises a lyocell fiber main body, nano inorganic powder and plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate.

As a preferred technical scheme:

the lyocell fiber containing the vegetable essential oil has a fineness of 1.2 to 3.5dtex (measured according to GB/T14335), a dry breaking strength of 2.0 to 4.5cN/dtex, a dry elongation at break of 11 to 20%, a wet breaking strength of 1.9 to 4.0cN/dtex (measured according to GB/T14337 for dry, wet and dry elongation at break), and a saturated moisture regain of 5 to 13%.

After the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile tests, the elution rate of the plant essential oil is 30-50%, and the calculation formula is as follows:

the method for testing the quality of the essential oil contained in the fiber comprises the following steps: eluting plant essential oil existing in the fiber by adopting an organic solvent to obtain a plant essential oil solution, testing the content of the plant essential oil in the solution by an ultraviolet visible spectrometer, and converting to obtain the quality of the essential oil contained in the fiber.

The principle of the invention is as follows:

according to the invention, the nano inorganic powder subjected to hydrophobic modification treatment is adopted, so that oily plant essential oil can be adsorbed, and solid nano particles (namely nano inorganic powder) attached with the plant essential oil exist in the fiber during forming, so that the rapid loss of the essential oil can be effectively avoided; because the shearing rate of the spinning solution in the pipeline flow field along the pipeline wall is highest, the nano inorganic powder adsorbing the plant essential oil flows into the spinning trickle according to the principle of lowest energy, and more nano inorganic powder exists in the fiber, so that the loss of the plant essential oil is reduced. Because the inorganic powder is in a nanometer scale, the particle size is one order of magnitude smaller than that of a micrometer-scale spinneret plate hole, and the phenomena of filament breakage and the like caused by blockage of the spinneret plate hole are avoided.

According to the invention, the plant essential oil/nano inorganic powder mixture and the cellulose/cellulose acetate/NMMO/aqueous solution (namely the functional mother solution base solution) are mixed to prepare the plant essential oil functional mother solution, and a strong shearing effect exists in the preparation process of the plant essential oil functional mother solution, so that the cellulose and the plant essential oil can be uniformly dispersed, and the damage of the addition of the plant essential oil to a fiber structure is reduced; the functional mother liquor of the plant essential oil contains a certain amount of cellulose acetate, the molecular chain of the cellulose acetate has acetate groups, and the steric hindrance is greater than the hydroxyl on the molecular chain of the cellulose, so that the crystallization performance of the cellulose acetate is weaker than that of the cellulose, the crystallinity of the fiber is reduced, the increase of amorphous areas on the supermolecule scale of the fiber can cause more micropores on the dimension of a micro-nano structure, the micropores contain the plant essential oil, the function of coating the plant essential oil is achieved, in the forming process, the coated plant essential oil is not easy to run off, in the using process, the plant essential oil can be released only by penetrating through a fiber matrix, and the slow release time is longer.

According to the invention, the plant essential oil functional mother liquor and the lyocell spinning solution are mixed to prepare the lyocell spinning solution containing the plant essential oil, and then spinning is carried out, so that the viscosity difference between the plant essential oil functional mother liquor and the lyocell spinning solution is small, the influence of the viscosity difference of the spinning solution on the stability of a spinning system is avoided, and the conventional lyocell spinning process can meet the production requirement.

The invention also carries out organic silicon water repellent finishing on the prepared lyocell fiber containing the plant essential oil, so that the cellulose fiber has a certain hydrophobic coating and can slow down the release of the plant essential oil.

Advantageous effects

(1) According to the preparation method of the lyocell fiber containing the plant essential oil, the loss of the plant essential oil is small in the forming process;

(2) according to the preparation method of the lyocell fiber containing the vegetable essential oil, disclosed by the invention, the additive is simple in component and does not react with NMMO (N-methyl-MO), so that the stable and durable operation of a spinning system can be ensured;

(3) the preparation method of the plant essential oil-containing lyocell fiber combines the advantages of fiber forming and after finishing, and the fiber forming and after finishing integrated technology is applied to the preparation of the plant essential oil-containing lyocell fiber, so that the release of the plant essential oil can be effectively slowed down;

(4) the lyocell fiber containing the plant essential oil prepared by the method has good moisture regain and excellent mechanical property.

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

A method for preparing lyocell fiber containing vegetable essential oil comprises the following steps:

(1) uniformly mixing plant essential oil (mixture of oleum Lavandula Angustifolia and oleum Armeniacae amarum at a mass ratio of 1: 1) and nanometer inorganic powder (hydrophobic fumed silica, model H15, Germany Wake) to obtain plant essential oil/nanometer inorganic powder mixture;

in the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 10 percent;

(2) mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base liquor by adopting a screw extruder to prepare plant essential oil functional mother liquor with the viscosity of 14000 Pa.s;

wherein the functional mother solution base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 900, and the mass fraction of the cellulose is 6%; the esterification degree of the cellulose acetate is 1, and the mass fraction of the cellulose acetate is 1%; the NMMO accounts for 77% of the mass fraction;

the mass ratio of the functional mother liquor base liquid to the plant essential oil/nano inorganic powder mixture is 3: 1;

mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base solution at 90 deg.C for 10 min;

(3) mixing the plant essential oil functional mother liquor with a Lyocell spinning solution with the viscosity of 15000Pa & s to prepare a Lyocell spinning solution containing plant essential oil, and spinning;

the lyocell spinning solution consists of cellulose, NMMO and water; the polymerization degree of the cellulose is 600;

in the lyocell spinning solution, the mass fraction of cellulose is 15%, and the mass fraction of NMMO is 77%;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 3;

the spinning process comprises the following steps: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 10%, and the temperature of the coagulating bath is 15 ℃;

(4) carrying out after-treatment on the fibers by adopting an organic silicon finishing agent to prepare the lyocell fibers containing the vegetable essential oil;

the organic silicon finishing agent consists of 2 weight percent of methyl hydrogen-containing silane emulsion, 5 weight percent of hydroxyl silane emulsion, 1 weight percent of aminated epoxy cross-linking agent, 0.8 weight percent of crystalline zinc acetate, 0.4 weight percent of zirconium oxychloride, 0.3 weight percent of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: soaking (controlling the liquid carrying rate to be 60%) → drying (the drying temperature is 100 ℃) → baking (the baking temperature is 120 ℃, and the time is 5min) → water washing → oiling → drying.

The prepared lyocell fiber containing the plant essential oil mainly comprises a lyocell fiber main body, nano inorganic powder and the plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate; the titer of the lyocell fiber containing the vegetable essential oil is 1.2dtex, the dry breaking strength is 4.5cN/dtex, the dry elongation at break is 11%, the wet breaking strength is 4.0cN/dtex, and the saturated moisture regain is 9%; after the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile test, the elution rate of the plant essential oil is 30 percent.

Comparative example 1

A method for preparing lyocell fiber containing vegetable essential oil, which is basically the same as example 1, except that the nano inorganic powder in the step (1) is not subjected to hydrophobic modification treatment.

The fineness of the obtained lyocell fiber containing the plant essential oil is 1.2dtex, the dry breaking strength is 4.0cN/dtex, the dry breaking elongation is 10%, the wet breaking strength is 3.5cN/dtex, the saturated moisture regain is 10%, and the elution rate of the plant essential oil is 53%.

Compared with example 1, the breaking strength of comparative example 1 is smaller than that of example 1, and the elution rate of the plant essential oil of comparative example 1 is higher than that of example 1, because the inorganic powder without hydrophobic modification has hydrophilic property, cannot effectively adsorb the plant essential oil, and the plant essential oil is greatly lost during the forming and using processes.

Comparative example 2

A method for preparing lyocell fiber containing vegetable essential oil, which is substantially the same as that of example 1, except that the functional mother liquor base solution in the step (2) consists of cellulose, NMMO and water, and the mass of the cellulose in the functional mother liquor base solution is the sum of the mass of the cellulose and the mass of the cellulose acetate in the functional mother liquor base solution in example 1.

The fineness of the obtained lyocell fiber containing the plant essential oil is 1.2dtex, and the elution rate of the plant essential oil is 35 percent.

The elution rate of the plant essential oil of comparative example 2 is higher than that of example 1, compared to example 1, because the absence of cellulose acetate in comparative example 2 results in a decrease in micropores, resulting in an increase in the elution rate of the plant essential oil.

Comparative example 3

A method for preparing lyocell fiber containing plant essential oil, which is substantially the same as that of example 1, except that in the functional mother liquor base solution in the step (2), the mass fraction of cellulose is 12%, the mass fraction of cellulose acetate is 3%, and the viscosity of the finally prepared functional mother liquor of plant essential oil is 25000Pa · s.

Experiments show that the finally prepared lyocell spinning solution containing the plant essential oil cannot be extruded normally, and the stability of a spinning system is influenced, because the viscosity of the polymer in the plant essential oil functional mother liquor and the lyocell spinning solution in the comparative example 3 is too different, the normal operation of the spinning system is influenced, and fibers are difficult to prepare.

Example 2

A method for preparing lyocell fiber containing vegetable essential oil comprises the following steps:

(1) uniformly mixing plant essential oil (mixture of rosemary oil and jojoba oil at a mass ratio of 1: 1) and nanometer inorganic powder (German Wake, hydrophobic fumed silica, model H20) to obtain plant essential oil/nanometer inorganic powder mixture;

in the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 14 percent;

(2) mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base liquor by adopting a screw extruder to prepare plant essential oil functional mother liquor with the viscosity of 13500Pa & s;

wherein the functional mother solution base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 850, and the mass fraction of the cellulose is 7%; the esterification degree of the cellulose acetate is 1.5, and the mass fraction of the cellulose acetate is 1.2%; the NMMO accounts for 76% by mass;

the mass ratio of the functional mother liquor base liquid to the plant essential oil/nano inorganic powder mixture is 2.5: 1;

mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base solution at 92 deg.C for 9 min;

(3) mixing the plant essential oil functional mother liquor with a Lyocell spinning solution with the viscosity of 14000Pa & s to prepare a Lyocell spinning solution containing plant essential oil, and spinning;

the lyocell spinning solution consists of cellulose, NMMO and water; the degree of polymerization of the cellulose is 500;

in the lyocell spinning solution, the mass fraction of cellulose is 13%, and the mass fraction of NMMO is 76%;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 2.5;

the spinning process comprises the following steps: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 12%, and the temperature of the coagulating bath is 17 ℃;

(4) carrying out after-treatment on the fibers by adopting an organic silicon finishing agent to prepare the lyocell fibers containing the vegetable essential oil;

the organic silicon finishing agent consists of 2 weight percent of methyl hydrogen-containing silane emulsion, 5 weight percent of hydroxyl silane emulsion, 1 weight percent of aminated epoxy cross-linking agent, 0.8 weight percent of crystalline zinc acetate, 0.5 weight percent of zirconium oxychloride, 0.3 weight percent of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: soaking (the liquid carrying rate is controlled to be 65%) → drying (the drying temperature is 100 ℃) → baking (the baking temperature is 125 ℃, and the time is 5min) → water washing → oiling → drying.

The prepared lyocell fiber containing the plant essential oil mainly comprises a lyocell fiber main body, nano inorganic powder and the plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate; the titer of the lyocell fiber containing the vegetable essential oil is 1.5dtex, the dry breaking strength is 4cN/dtex, the dry elongation at break is 13%, the wet breaking strength is 3.6cN/dtex, and the saturated moisture regain is 8%; after the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile test, the elution rate of the plant essential oil is 35 percent.

Example 3

A method for preparing lyocell fiber containing vegetable essential oil comprises the following steps:

(1) uniformly mixing plant essential oil (mixture of lemon oil and grape seed oil at a mass ratio of 1: 1) and nanometer inorganic powder (silicon dioxide AEROSIL R812S) to obtain plant essential oil/nanometer inorganic powder mixture;

in the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 18 percent;

(2) mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base liquid by adopting a screw extruder to prepare plant essential oil functional mother liquor with the viscosity of 13000 Pa.s;

wherein the functional mother solution base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 800, and the mass fraction of the cellulose is 8%; the esterification degree of the cellulose acetate is 1.5, and the mass fraction of the cellulose acetate is 1.3%; the NMMO accounts for 75% by mass;

the mass ratio of the functional mother liquor base liquid to the plant essential oil/nano inorganic powder mixture is 2.2: 1;

mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base solution at 94 deg.C for 8 min;

(3) mixing the plant essential oil functional mother liquor with a Lyocell spinning solution with the viscosity of 13200 Pa.s to prepare a Lyocell spinning solution containing plant essential oil, and spinning;

the lyocell spinning solution consists of cellulose, NMMO and water; the polymerization degree of the cellulose is 400;

in the lyocell spinning solution, the mass fraction of cellulose is 11%, and the mass fraction of NMMO is 75%;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 2.2;

the spinning process comprises the following steps: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 14%, and the temperature of the coagulating bath is 19 ℃;

(4) carrying out after-treatment on the fibers by adopting an organic silicon finishing agent to prepare the lyocell fibers containing the vegetable essential oil;

the organic silicon finishing agent consists of 3 wt% of methyl hydrogen-containing silane emulsion, 6 wt% of hydroxyl silane emulsion, 1 wt% of aminated epoxy cross-linking agent, 0.9 wt% of crystalline zinc acetate, 0.5 wt% of zirconium oxychloride, 0.4 wt% of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: soaking (the liquid carrying rate is controlled to be 65%) → drying (the drying temperature is 101 ℃) → baking (the baking temperature is 125 ℃, and the time is 5min) → water washing → oiling → drying.

The prepared lyocell fiber containing the plant essential oil mainly comprises a lyocell fiber main body, nano inorganic powder and the plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate; the titer of the lyocell fiber containing the vegetable essential oil is 1.8dtex, the dry breaking strength is 3.7cN/dtex, the dry elongation at break is 15%, the wet breaking strength is 3.2cN/dtex, and the saturated moisture regain is 7%; after the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile test, the elution rate of the plant essential oil is 37 percent.

Example 4

A method for preparing lyocell fiber containing vegetable essential oil comprises the following steps:

(1) uniformly mixing plant essential oil (mixture of clove oil and wheat germ oil with a mass ratio of 1: 1) and nanometer inorganic powder (silicon dioxide AEROSIL R8200) to obtain plant essential oil/nanometer inorganic powder mixture;

in the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 20 percent;

(2) mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base liquor by adopting a screw extruder to prepare the plant essential oil functional mother liquor with the viscosity of 12000 Pa.s;

wherein the functional mother solution base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 700, and the mass fraction of the cellulose is 9%; the esterification degree of the cellulose acetate is 1.5, and the mass fraction of the cellulose acetate is 1.5%; the NMMO accounts for 76% by mass;

the mass ratio of the functional mother liquor base liquid to the plant essential oil/nano inorganic powder mixture is 2: 1;

mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base solution at 96 deg.C for 7 min;

(3) mixing the plant essential oil functional mother liquor with a Lyocell spinning solution with the viscosity of 12500Pa & s to prepare a Lyocell spinning solution containing plant essential oil, and spinning;

the lyocell spinning solution consists of cellulose, NMMO and water; the polymerization degree of the cellulose is 450;

in the lyocell spinning solution, the mass fraction of cellulose is 10 percent, and the mass fraction of NMMO is 76 percent;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 2;

the spinning process comprises the following steps: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 16%, and the temperature of the coagulating bath is 21 ℃;

(4) carrying out after-treatment on the fibers by adopting an organic silicon finishing agent to prepare the lyocell fibers containing the vegetable essential oil;

the organic silicon finishing agent consists of 4 wt% of methyl hydrogen-containing silane emulsion, 7 wt% of hydroxyl silane emulsion, 2 wt% of aminated epoxy cross-linking agent, 1.1 wt% of crystalline zinc acetate, 0.7 wt% of zirconium oxychloride, 0.5 wt% of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: soaking (the liquid carrying rate is controlled to be 70%) → drying (the drying temperature is 103 ℃) → baking (the baking temperature is 130 ℃, and the time is 4min) → water washing → oiling → drying.

The prepared lyocell fiber containing the plant essential oil mainly comprises a lyocell fiber main body, nano inorganic powder and the plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate; the titer of the lyocell fiber containing the vegetable essential oil is 2.3dtex, the dry breaking strength is 3.4cN/dtex, the dry elongation at break is 17%, the wet breaking strength is 2.9cN/dtex, and the saturated moisture regain is 5%; after the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile test, the elution rate of the plant essential oil is 36 percent.

Example 5

A method for preparing lyocell fiber containing vegetable essential oil comprises the following steps:

(1) uniformly mixing plant essential oil (mixture of peppermint oil and sweet almond oil with the mass ratio of 1: 1) and nano inorganic powder (New material of Xuancheng crystal Rui Co., Ltd., hydrophobic nano titanium dioxide rutile VK-T02SG) to obtain plant essential oil/nano inorganic powder mixture;

in the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 22 percent;

(2) mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base liquid by adopting a screw extruder to prepare the plant essential oil functional mother liquor with the viscosity of 11000 Pa.s;

wherein the functional mother solution base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 650, and the mass fraction of the cellulose is 9%; the esterification degree of the cellulose acetate is 2, and the mass fraction of the cellulose acetate is 1.7%; the NMMO accounts for 77% of the mass fraction;

the mass ratio of the functional mother liquor base liquid to the plant essential oil/nano inorganic powder mixture is 1.5: 1;

mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base solution at 98 deg.C for 6 min;

(3) mixing the plant essential oil functional mother liquor with a Lyocell spinning solution with the viscosity of 11500Pa & s to prepare a Lyocell spinning solution containing plant essential oil, and spinning;

the lyocell spinning solution consists of cellulose, NMMO and water; the degree of polymerization of the cellulose is 500;

in the lyocell spinning solution, the mass fraction of cellulose is 9%, and the mass fraction of NMMO is 77%;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 1.5;

the spinning process comprises the following steps: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 18 percent, and the temperature of the coagulating bath is 22 ℃;

(4) carrying out after-treatment on the fibers by adopting an organic silicon finishing agent to prepare the lyocell fibers containing the vegetable essential oil;

the organic silicon finishing agent consists of 4 wt% of methyl hydrogen-containing silane emulsion, 8 wt% of hydroxyl silane emulsion, 2 wt% of aminated epoxy cross-linking agent, 1.2 wt% of crystalline zinc acetate, 0.8 wt% of zirconium oxychloride, 0.5 wt% of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: soaking (the liquid carrying rate is controlled to be 80%) → drying (the drying temperature is 104 ℃) → baking (the baking temperature is 135 ℃ and the time is 3min) → water washing → oiling → drying.

The prepared lyocell fiber containing the plant essential oil mainly comprises a lyocell fiber main body, nano inorganic powder and the plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate; the titer of the lyocell fiber containing the vegetable essential oil is 3dtex, the dry breaking strength is 3cN/dtex, the dry breaking elongation is 18%, the wet breaking strength is 2.4cN/dtex, and the saturated moisture regain is 6%; after the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile test, the elution rate of the plant essential oil is 39 percent.

Example 6

A method for preparing lyocell fiber containing vegetable essential oil comprises the following steps:

(1) uniformly mixing plant essential oil (mixture of cinnamon oil and jojoba oil at a mass ratio of 1: 1) and inorganic nanopowder (New material of Xuancheng crystal Rui Co., Ltd., hydrophobic nanometer titanium dioxide rutile VK-T02SG) to obtain plant essential oil/inorganic nanopowder mixture;

in the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 25 percent;

(2) mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base liquor by adopting a screw extruder to prepare plant essential oil functional mother liquor with the viscosity of 9000 Pa.s;

wherein the functional mother solution base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 600, and the mass fraction of the cellulose is 10%; the esterification degree of the cellulose acetate is 2, and the mass fraction of the cellulose acetate is 2%; the NMMO accounts for 75% by mass;

the mass ratio of the functional mother liquor base liquid to the plant essential oil/nano inorganic powder mixture is 1: 1;

mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base solution at 99 deg.C for 6 min;

(3) mixing the plant essential oil functional mother liquor with a Lyocell spinning solution with the viscosity of 9500Pa & s to prepare a Lyocell spinning solution containing plant essential oil, and spinning;

the lyocell spinning solution consists of cellulose, NMMO and water; the degree of polymerization of cellulose is 550;

in the lyocell spinning solution, the mass fraction of cellulose is 8 percent, and the mass fraction of NMMO is 75 percent;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 1;

the spinning process comprises the following steps: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulating bath is 22%, and the temperature of the coagulating bath is 24 ℃;

(4) carrying out after-treatment on the fibers by adopting an organic silicon finishing agent to prepare the lyocell fibers containing the vegetable essential oil;

the organic silicon finishing agent consists of 4 wt% of methyl hydrogen-containing silane emulsion, 8 wt% of hydroxyl silane emulsion, 2 wt% of aminated epoxy cross-linking agent, 1.2 wt% of crystalline zinc acetate, 0.8 wt% of zirconium oxychloride, 0.6 wt% of monoethanolamine and the balance of water;

the process flow of after-finishing is as follows: soaking (the liquid carrying rate is controlled to be 80%) → drying (the drying temperature is 105 ℃) → baking (the baking temperature is 140 ℃, and the time is 3min) → water washing → oiling → drying.

The prepared lyocell fiber containing the plant essential oil mainly comprises a lyocell fiber main body, nano inorganic powder and the plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate; the titer of the lyocell fiber containing the vegetable essential oil is 3.5dtex, the dry breaking strength is 2cN/dtex, the dry elongation at break is 20%, the wet breaking strength is 2.5cN/dtex, and the saturated moisture regain is 7%; after the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile test, the elution rate of the plant essential oil is 41 percent.

Example 7

A method for preparing lyocell fiber containing vegetable essential oil comprises the following steps:

(1) uniformly mixing plant essential oil (a mixture of thyme oil and grape seed oil in a mass ratio of 1: 1) and nano inorganic powder (a mixture of silicon dioxide and titanium dioxide in a mass ratio of 1:1, wherein the type of the silicon dioxide is German Wake hydrophobic type gas phase method silicon dioxide H18, and the type of the titanium dioxide is Xuancheng New Crystal Material Co., Ltd VK-T06S) to prepare a plant essential oil/nano inorganic powder mixture;

in the mixture of the plant essential oil and the nano inorganic powder, the mass fraction of the nano inorganic powder is 20 percent;

(2) mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base liquor by adopting a screw extruder to prepare the plant essential oil functional mother liquor with the viscosity of 10500 Pa.s;

wherein the functional mother solution base solution consists of cellulose, cellulose acetate, NMMO and water; the polymerization degree of the cellulose is 700, and the mass fraction of the cellulose is 8%; the esterification degree of the cellulose acetate is 2, and the mass fraction of the cellulose acetate is 2%; the NMMO accounts for 76% by mass;

the mass ratio of the functional mother liquor base liquid to the plant essential oil/nano inorganic powder mixture is 2: 1;

mixing the plant essential oil/nano inorganic powder mixture with the functional mother liquor base solution at 100 deg.C for 5 min;

(3) mixing the plant essential oil functional mother liquor with a Lyocell spinning solution with the viscosity of 11000 Pa.s to prepare a Lyocell spinning solution containing plant essential oil, and spinning;

the lyocell spinning solution consists of cellulose, NMMO and water; the polymerization degree of the cellulose is 600;

in the lyocell spinning solution, the mass fraction of cellulose is 10 percent, and the mass fraction of NMMO is 76 percent;

the mass ratio of the plant essential oil functional mother liquor to the lyocell spinning solution is 1: 2;

the spinning process comprises the following steps: extruding a lyocell spinning solution containing plant essential oil through a spinning assembly, allowing the extruded lyocell spinning solution to enter a coagulating bath through an air layer, and sequentially winding, washing and cutting off; the mass fraction of NMMO in the coagulation bath was 25%, and the temperature of the coagulation bath was 25 ℃.

The prepared lyocell fiber containing the plant essential oil mainly comprises a lyocell fiber main body, nano inorganic powder and the plant essential oil; the plant essential oil is attached to the nano inorganic powder, the nano inorganic powder is dispersed in the lyocell fiber main body, and the lyocell fiber main body is composed of cellulose and cellulose acetate; the titer of the lyocell fiber containing the vegetable essential oil is 2dtex, the dry breaking strength is 2.5cN/dtex, the dry elongation at break is 15%, the wet breaking strength is 1.9cN/dtex, and the saturated moisture regain is 13%; after the lyocell fiber containing the plant essential oil is washed by water for 10 times according to the household washing and drying program GB/T8629-2017 for textile test, the elution rate of the plant essential oil is 50 percent.