CN106149080B - A kind of preparation method of cellulose/calamine composite fibre - Google Patents

Abstract

The invention relates to a preparation method of cellulose/calamine composite fiber, comprising the following steps: dissolving cellulose ester with a cellulose solvent to obtain a carrier solution of calamine powder; Function, the calamine powder is mixed with the carrier solution to obtain the calamine mother liquor; the calamine mother liquor is injected into the cellulose spinning solution in the form of online addition, and the spinning solution is extruded, solidified, formed and drawn. A cellulose/calamine composite fiber was prepared. Aiming at the problem that calamine powder is difficult to mix evenly with high-viscosity spinning solution, the invention adopts the method of injecting calamine mother liquor into spinning solution, and then spinning and forming to prepare cellulose/calamine composite fiber. The mother liquid carrier used in the present invention is formed along with the solidification of the fiber, and no additional auxiliary agent enters into the solvent and coagulation bath system. The forming method of the invention is simple, flexible and efficient, and can realize the production of cellulose/calamine composite fiber based on a conventional production line.

Description

A kind of preparation method of cellulose/calamine composite fiber

technical field

The invention relates to the field of regenerated fibers, in particular to a preparation method of cellulose/calamine composite fibers.

Background technique

Cellulose fibers such as cotton, viscose fiber, and lyocell fiber have excellent skin-friendly properties and are widely used in intimate clothing. In order to increase the function of cellulose fiber, patent ZL201010511031.5 (calamine cellulose fiber and its preparation method) proposes a preparation method of functional cellulose fiber, the specific method is to mix calamine slurry with cellulose/ion The liquid spinning solution is mixed, and the cellulose/calamine composite fiber is prepared by wet spinning. Because calamine has a therapeutic effect on various contact dermatitis, functional fibers can prevent the occurrence of skin diseases, and can also relieve symptoms of acute itching skin diseases such as urticaria and prickly heat.

When mixing calamine powder such as calamine with cellulose spinning solution, the mixing uniformity of the two is the primary consideration. Due to the high viscosity of the cellulose solution, the powder dispersion process is difficult and requires high equipment. In addition, there are also problems that the powder is easy to deposit, agglomerate, and unevenly mixed, resulting in the clogging of the spinneret hole and the instability of the fiber performance. In order to improve the dispersion uniformity of calamine and spinning dope, patent ZL201010511031.5 premixes calamine with amine cationic surfactant, silicon cationic surfactant and sodium tripolyphosphate to make a suspension Or calamine slurry in emulsion state. Mixing suspensions, emulsions and cellulose spinning solutions can improve the dispersion uniformity of functional additives. However, additives such as surfactants will enter the coagulation bath, which will affect the normal recovery of solvents and coagulants and increase recovery costs. The additives remaining in the fiber will also affect the physical and chemical properties of the fiber, and there is also the possibility of additive leakage during use.

How to efficiently realize the uniform dispersion of calamine powder and reduce the interference of calamine powder addition process on the original forming process is the technical bottleneck that needs to be broken through in the production of cellulose/calamine composite fiber.

Contents of the invention

The present invention aims at the deficiencies of the prior art, and provides a preparation method of cellulose/calamine composite fiber, in which calamine powder and cellulose ester solution are uniformly mixed to obtain calamine mother liquor, and calamine The mother liquor is injected into the cellulose spinning liquid by the method of online addition, and then spun and formed to obtain the cellulose/calamine composite fiber.

A kind of preparation method of cellulose/calamine composite fiber of the present invention, comprises the following steps:

(1) adopt cellulose solvent to dissolve cellulose ester, make the carrier solution of calamine powder;

(2) stirring and mixing the calamine powder and the carrier solution to obtain the calamine mother liquor;

(3) Inject the calamine mother liquor into the cellulose spinning solution to obtain a functional spinning solution, which is then extruded

Extraction, coagulation and drafting to obtain cellulose/calamine composite fibers.

The preparation method of the above-mentioned cellulose/calamine composite fiber, the cellulose ester is cellulose acetate, cellulose acetate propionate or cellulose acetate butyrate, and the degree of polymerization of the cellulose ester is 200-1000 , the total degree of esterification is 2.3-2.5; the degree of polymerization of the cellulose raw material in the cellulose spinning solution is 500-1500.

According to the above-mentioned preparation method of cellulose/calamine composite fiber, the average particle diameter of the calamine powder is less than 0.2 μm.

The preparation method of the above-mentioned cellulose/calamine composite fiber, the cellulose solvent is N-methylmorpholine-N-oxide water or ionic liquid;

The N-methylmorpholine-N-oxide/water system, wherein the proportion of water is less than 15wt%;

The ionic liquid is 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate or 1-butyl-3-methylimidazolium bromide.

The preparation method of the above-mentioned cellulose/calamine composite fiber, the concentration of cellulose ester in the carrier solution is 6-15wt%; the mass ratio of the cellulose ester to calamine powder is 1-10 : 1; the concentration of cellulose raw material in the cellulose spinning solution is 6～15wt%.

The preparation method of the above-mentioned cellulose/calamine composite fiber, the equipment used for the stirring is a screw extruder or a kneader, the speed of the stirring is 100-300 rev/min, and the duration of the stirring is 0.5-1 hour.

The preparation method of the cellulose/calamine composite fiber as described above, the mode of injecting the calamine mother liquor in the cellulose spinning solution is that the calamine mother liquor is injected into the cellulose spinning solution in the mode of online addition, Specifically, an on-line addition device for calamine mother liquor is installed on the cellulose spinning liquor delivery pipeline on the production line, wherein the mass ratio of cellulose spinning liquor to calamine mother liquor is 3-20:1.

In the preparation method of the cellulose/calamine composite fiber described above, the process for preparing the cellulose/calamine composite fiber from the functional spinning solution is a wet spinning process or a dry-spray wet spinning process.

The cellulose/calamine composite fiber prepared by the preparation method of the above-mentioned cellulose/calamine composite fiber, the monofilament fineness of the cellulose/calamine composite fiber is 0.9-4.8dtex, and the dry state breaking strength It is 1.7-4.5cN/dtex.

The above-mentioned cellulose/calamine composite fiber has auxiliary therapeutic effect on skin itching and skin inflammation.

Principle of the present invention:

Cellulose is composed of D-glucopyranose group, which belongs to the rigid chain structure, and the hydroxyl groups on the cellulose molecular chain form hydrogen bonds between the molecular chains and the molecular chains. Due to the characteristics of the molecular structure of cellulose, the viscosity of the cellulose solution is relatively high. For example, the cellulose/NMMO/H ₂ O solution with a degree of cellulose polymerization of 569 and a concentration of 12.9 wt% has a zero-shear viscosity at 85°C It is 8670Pa.s; the degree of cellulose polymerization is 569, the concentration is 10.4wt% cellulose/1-butyl-3-methylimidazolium chloride salt ([BMIM]Cl) solution, the zero-shear viscosity when the temperature is 85°C Reach 7920Pa.s (Kosan B, Michels C, MeisterF. Dissolution and forming of cellulose with ionic liquids [J]. Cellulose, 2008, 15 (1): 59-66.). The high viscosity makes it difficult for calamine powder to disperse evenly in the cellulose solution, and the requirements for mixing equipment are also relatively strict.

Since the number of hydroxyl groups on the cellulose ester molecular chain is less than that on the cellulose molecular chain, the interaction between the cellulose ester molecular chain and the molecular chain is also reduced, so the viscosity of the cellulose ester solution is smaller than that of the cellulose solution. . In addition, the structures of cellulose ester and cellulose are almost identical, and the two can achieve mutual solubility at the molecular level.

Based on this, the present invention selects cellulose ester as the carrier of the calamine powder, and as a bridge for the uniform mixing of the calamine powder and the cellulose spinning solution. Utilizing the characteristic that cellulose ester is easier to mix evenly with calamine powder and cellulose solution, it acts as an intermediary to promote the mixing of calamine powder and cellulose spinning solution.

Beneficial effect:

(1) Utilizing the advantage that the viscosity of cellulose ester solution is lower than that of cellulose spinning solution, and it is easier to mix evenly with calamine powder, cellulose ester is selected as the matrix of calamine mother liquor, and calamine powder dispersion Uniform and stable calamine mother liquor. The calamine mother liquor can be injected into the spinning solution delivery system of conventional regenerated cellulose fibers through an online adding device, so that cellulose/calamine composite fibers can be manufactured conveniently and flexibly.

(2) The molecular structure of cellulose ester is similar to that of cellulose, and the two can achieve mutual solubility at the molecular level. The coagulation process is coagulated together with the cellulose and does not enter the coagulation bath, no additional additives enter the coagulation bath, and do not increase the burden of solvent and coagulation bath recovery. According to the invention, the production of the cellulose/calamine composite fiber can be realized only by adding an online adding device on the conventional regenerated cellulose fiber production line, and the method is simple and operable.

(3) The cellulose/calamine composite fiber can prevent the occurrence of skin diseases, and has an auxiliary therapeutic effect on skin itching and skin inflammation.

Detailed ways

The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Adopting cellulose solvent N-methylmorpholine-N-oxide (NMMO)/water (wherein the proportion that water accounts for is 13.8wt%) dissolving degree of polymerization is 200, and the cellulose acetate of total esterification degree is 2.3, prepares The carrier solution of calamine powder with a cellulose acetate concentration of 6wt% is obtained; then the calamine powder and the carrier solution with an average particle diameter of 0.19 μm are stirred and mixed by a screw extruder, wherein the stirring speed is 100 rpm / minute, the duration of stirring is 0.5 hours, the mass ratio of cellulose acetate and calamine powder is 1:1, and the calamine mother liquor is obtained; finally, the calamine mother liquor is injected into the method of online addition and the degree of polymerization is 500 , the concentration is 6wt% in the cellulose spinning liquid, specifically install the calamine mother liquor on-line adding device on the cellulose spinning liquid conveying pipeline on the production line, wherein the quality of the cellulose spinning liquid and the calamine mother liquor The ratio is 3:1, and the functional spinning solution is prepared, and then the cellulose/calamine composite fiber is obtained through the steps of extrusion, coagulation and drawing in the wet spinning process.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 0.9 dtex, and the dry breaking strength is 1.7 cN/dtex.

Example 2

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Adopt cellulose solvent N-methylmorpholine-N-oxide oxide (NMMO)/water (wherein the proportion that water accounts for is 13.4wt%) dissolving degree of polymerization is 1000, and total esterification degree is the cellulose acetate propionate of 2.5 , the obtained cellulose acetate propionate concentration is the carrier solution of the calamine powder of 15wt%; Then the calamine powder and the carrier solution with an average particle diameter of 0.18 μm are stirred and mixed by a kneader, wherein the stirring rate is 300 rpm, stirring for 1 hour, the mass ratio of cellulose acetate propionate to calamine powder is 9:1, and the calamine mother liquor is prepared; finally, the calamine mother liquor is injected online In the cellulose spinning solution with a degree of polymerization of 1500 and a concentration of 15wt%, specifically, an on-line addition device for calamine mother liquor is installed on the cellulose spinning solution delivery pipeline on the production line, wherein the cellulose spinning solution and calamine The mass ratio of the stone mother liquor is 20:1, and the functional spinning solution is prepared, and then the cellulose/calamine composite fiber is obtained through the steps of extrusion, coagulation and drawing in the dry-jet wet spinning process.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 4.8dtex, and the dry breaking strength is 1.7cN/dtex.

Example 3

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-butyl-3-methylimidazolium chloride salt to dissolve the cellulose acetate butyrate with a degree of polymerization of 300 and a total degree of esterification of 2.4 to prepare calamine with a concentration of cellulose acetate butyrate of 7 wt%. The carrier solution of the powder; then the calamine powder and the carrier solution with an average particle size of 0.19 μm are stirred and mixed with a screw extruder, wherein the stirring speed is 200 rpm, and the stirring time is 0.6 hours. The mass ratio of acid cellulose and calamine powder is 10:1, and the calamine mother liquor is obtained; finally, the calamine mother liquor is injected into the cellulose spinning with a degree of polymerization of 600 and a concentration of 8wt% in the form of online addition. Specifically, an on-line addition device for calamine mother liquor is installed on the cellulose spinning liquor delivery pipeline on the production line, wherein the mass ratio of cellulose spinning liquor to calamine mother liquor is 7:1, and functional The spinning solution is then subjected to the extrusion, coagulation and drawing steps of the wet spinning process to obtain the cellulose/calamine composite fiber.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 0.9 dtex, and the dry breaking strength is 4.5 cN/dtex.

Example 4

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-ethyl-3-methylimidazole acetate to dissolve the cellulose acetate butyrate with a degree of polymerization of 400 and a total degree of esterification of 2.35 to prepare a cellulose acetate butyrate concentration of 8 wt% calamari The carrier solution of the stone powder; then the calamine powder and the carrier solution with an average particle size of 0.192 μm are stirred and mixed with a kneader, wherein the stirring speed is 150 rpm, and the stirring time is 0.7 hours. Acetate butyric acid The mass ratio of cellulose to calamine powder is 5:1, and the calamine mother liquor is obtained; finally, the calamine mother liquor is injected into the cellulose spinning solution with a degree of polymerization of 900 and a concentration of 7wt% in the form of online addition. In particular, an on-line addition device for calamine mother liquor is installed on the cellulose spinning liquor delivery pipeline on the production line, wherein the mass ratio of cellulose spinning liquor to calamine mother liquor is 7:1, and the functional spinning The silk liquid is then subjected to the extrusion, coagulation and drawing steps in the dry-jet wet spinning process to obtain the cellulose/calamine composite fiber.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 2dtex, and the dry breaking strength is 3cN/dtex.

Example 5

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-ethyl-3-methylimidazole acetate to dissolve the cellulose acetate butyrate with a degree of polymerization of 400 and a total degree of esterification of 2.39 to prepare cellulose acetate butyrate with a concentration of 10 wt%. The carrier solution of the stone powder; then the calamine powder and the carrier solution with an average particle size of 0.189 μm are stirred and mixed with a screw extruder, wherein the stirring speed is 250 rpm, and the stirring time is 0.8 hours. The mass ratio of cellulose butyrate and calamine powder is 8:1, and the calamine mother liquor is obtained; finally, the calamine mother liquor is injected into the cellulose spinning with a degree of polymerization of 900 and a concentration of 9wt% in the mode of online addition. In the silk liquid, specifically, an on-line addition device for calamine mother liquor is installed on the cellulose spinning liquid delivery pipeline on the production line, wherein the mass ratio of cellulose spinning liquid to calamine mother liquor is 6:1, and the functional The cellulose/calamine composite fiber is obtained through the steps of extrusion, coagulation and drawing in the wet spinning process.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 2.8dtex, and the dry breaking strength is 3.5cN/dtex.

Example 6

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-butyl-3-methylimidazolium bromide to dissolve cellulose acetate butyrate with a degree of polymerization of 850 and a total degree of esterification of 2.3 to prepare calamine with a concentration of cellulose acetate butyrate of 11 wt%. The carrier solution of the powder; then the calamine powder and the carrier solution with an average particle size of 0.191 μm are stirred and mixed with a screw extruder, wherein the stirring speed is 200 rpm, and the stirring time is 0.7 hours. The mass ratio of acid cellulose and calamine powder is 7:1, and the calamine mother liquor is obtained; finally, the calamine mother liquor is injected into the cellulose spinning with a degree of polymerization of 900 and a concentration of 12wt% in the mode of online addition. Specifically, an on-line addition device for calamine mother liquor is installed on the cellulose spinning liquor delivery pipeline on the production line, wherein the mass ratio of cellulose spinning liquor to calamine mother liquor is 12:1, and functional The spinning solution is then subjected to the extrusion, coagulation and drawing steps in the dry-jet wet spinning process to obtain the cellulose/calamine composite fiber.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 3.8dtex, and the dry breaking strength is 2.5cN/dtex.

Example 7

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-ethyl-3-methylimidazole acetate to dissolve the cellulose acetate propionate with a degree of polymerization of 450 and a total degree of esterification of 2.45 to prepare a cellulose acetate propionate concentration of 14 wt%. The carrier solution of the stone powder; then the calamine powder and the carrier solution with an average particle size of 0.19 μm are stirred and mixed with a screw extruder, wherein the stirring speed is 250 rpm, and the stirring time is 0.8 hours. The mass ratio of cellulose propionate and calamine powder is 3:1, and the calamine mother liquor is obtained; finally, the calamine mother liquor is injected into the cellulose spinning with a degree of polymerization of 1300 and a concentration of 14wt% in the mode of online addition. In the silk liquid, specifically, an on-line addition device for calamine mother liquor is installed on the cellulose spinning liquid delivery pipeline on the production line, wherein the mass ratio of cellulose spinning liquid to calamine mother liquor is 10:1, and the functional The cellulose/calamine composite fiber is obtained through the steps of extrusion, coagulation and drawing in the dry-jet wet spinning process.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 1.8dtex, and the dry breaking strength is 2.5cN/dtex.

Example 8

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-butyl-3-methylimidazolium bromide to dissolve cellulose acetate propionate with a degree of polymerization of 900 and a total degree of esterification of 2.3 to prepare calamine with a concentration of cellulose acetate propionate of 14wt% The carrier solution of the powder; then the calamine powder and the carrier solution with an average particle size of 0.194 μm are stirred and mixed with a kneader, wherein the stirring speed is 200 rpm, and the stirring time is 0.9 hours. Fiber acetate propionate The mass ratio of element and calamine powder is 6:1, and calamine mother liquor is obtained; Finally, the calamine mother liquor is injected into the cellulose spinning solution with a degree of polymerization of 1400 and a concentration of 12wt% in the mode of online addition. , specifically adding an on-line calamine mother liquor adding device to the cellulose spinning liquor delivery pipeline on the production line, wherein the mass ratio of the cellulose spinning liquor to the calamine mother liquor is 14:1 to obtain a functional spinning Liquid, and then through the extrusion, coagulation and drawing steps in the wet spinning process, the cellulose/calamine composite fiber is obtained.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 3dtex, and the dry breaking strength is 2.4cN/dtex.

Example 9

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-butyl-3-methylimidazolium bromide to dissolve cellulose acetate propionate with a degree of polymerization of 350 and a total degree of esterification of 2.3 to prepare calamine with a concentration of cellulose acetate propionate of 12 wt%. The carrier solution of the powder; then, the calamine powder and the carrier solution with an average particle size of 0.18 μm are stirred and mixed with a kneader, wherein the stirring speed is 200 rpm, and the stirring time is 0.9 hours. Fiber acetate propionate The mass ratio of element and calamine powder is 8:1, and the calamine mother liquor is obtained; Finally, the calamine mother liquor is injected into the cellulose spinning solution with a degree of polymerization of 800 and a concentration of 12wt% in the mode of online addition. , specifically to install a calamine mother liquor online adding device on the cellulose spinning liquor delivery pipeline on the production line, wherein the mass ratio of the cellulose spinning liquor to the calamine mother liquor is 5:1 to obtain a functional spinning liquid, and then through the extrusion, coagulation and drawing steps in the dry-jet wet spinning process, the cellulose/calamine composite fiber is obtained.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 3.2dtex, and the dry breaking strength is 2.1cN/dtex.

Example 10

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-butyl-3-methylimidazolium chloride to dissolve the cellulose acetate with a degree of polymerization of 600 and a total degree of esterification of 2.3 to prepare a carrier of calamine powder with a concentration of cellulose acetate of 13 wt%. solution; then the calamine powder with an average particle size of 0.195 μm and the carrier solution are stirred and mixed with a screw extruder, wherein the stirring speed is 200 rpm, and the stirring time is 0.7 hours, wherein the calamine powder The diameter of calamine is 1.2nm, and length is 4 μm, and the diameter of calamine powder is 28nm, and length 4.5 μm, and the mass ratio of cellulose acetate and calamine powder is 4:1, makes calamine mother liquor; The calamine mother liquor is injected into the cellulose spinning solution with a degree of polymerization of 1000 and a concentration of 8wt% in the form of online addition. Specifically, an online adding device for calamine mother liquor is installed on the cellulose spinning solution delivery pipeline on the production line. Wherein the mass ratio of cellulose spinning liquid and calamine mother liquor is 5:1, makes functional spinning liquid, then through extrusion in the wet spinning process, coagulation and drafting step, makes cellulose/ Calamine composite fibers.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 2.5 dtex, and the dry breaking strength is 3.4 cN/dtex.

Example 11

A kind of preparation method of cellulose/calamine composite fiber, comprises the steps:

Using cellulose solvent 1-butyl-3-methylimidazolium chloride salt to dissolve cellulose acetate with a degree of polymerization of 500 and a total degree of esterification of 2.44 to prepare a carrier of calamine powder with a concentration of cellulose acetate of 9 wt%. solution; then the calamine powder with an average particle size of 0.196 μm and the carrier solution are stirred and mixed with a screw extruder, wherein the stirring speed is 200 rpm, and the stirring time is 0.9 hours, wherein the calamine powder The diameter of the calamine powder is 1.8nm, and the length is 3.8 μm. The diameter of the calamine powder is 24nm, and the length is 4.1 μm. The mass ratio of cellulose acetate and the calamine powder is 10:1, so that the calamine mother liquor is obtained; The calamine mother liquor is injected into the cellulose spinning solution with a degree of polymerization of 1400 and a concentration of 14wt% in the form of online addition. Specifically, an online addition device for calamine mother liquor is installed on the cellulose spinning solution delivery pipeline on the production line , wherein the mass ratio of the cellulose spinning solution to the calamine mother liquor is 8:1, the functional spinning solution is obtained, and then through the extrusion, coagulation and drawing steps in the dry jet wet spinning process, the obtained Cellulose/calamine composite fiber.

Tests show that the monofilament fineness of the cellulose/calamine composite fiber is 0.9 dtex, and the dry breaking strength is 4 cN/dtex.

Claims (8)

1. a preparation method of cellulose/calamine composite fiber is characterized in that: comprise the steps: (1) adopt cellulose solvent to dissolve cellulose ester, make the carrier solution of calamine powder, described cellulose ester is cellulose acetate, cellulose acetate propionate or cellulose acetate butyrate, described cellulose ester The degree of polymerization is 200-450, and the total degree of esterification is 2.3-2.5; (2) stirring and mixing the calamine powder and the carrier solution to obtain the calamine mother liquor; (3) Inject the calamine mother liquor into the cellulose spinning solution to obtain a functional spinning solution, then extrude, coagulate and draw to obtain a cellulose/calamine composite fiber; the cellulose spinning The degree of polymerization of the cellulose raw material in the silk liquid is 500-1500. 2. The preparation method of cellulose/calamine composite fiber according to claim 1, characterized in that the average particle diameter of the calamine powder is less than 0.2 μm. 3. the preparation method of cellulose/calamine composite fiber according to claim 1, is characterized in that, described cellulose solvent is N-methylmorpholine-N-oxide compound/water or ionic liquid; In the N-methylmorpholine-N-oxide/water, the proportion of water is less than 15wt%; The ionic liquid is 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate or 1-butyl-3-methylimidazolium bromide. 4. the preparation method of cellulose/calamine composite fiber according to claim 1 is characterized in that, in the described carrier solution, the concentration of cellulose ester is 6～15wt%; Described cellulose ester and calamine The mass ratio of powder is 1-10:1; the concentration of cellulose raw material in the cellulose spinning liquid is 6-15wt%. 5. the preparation method of cellulose/calamine composite fiber according to claim 1 is characterized in that, the equipment that described stirring is used is screw extruder or kneader, and the speed of described stirring is 100-300 revs /min, the duration of the stirring is 0.5-1 hour. 6. the preparation method of cellulose/calamine composite fiber according to claim 1, is characterized in that, the mode that described calamine mother liquor injects in the cellulose spinning solution is that calamine mother liquor is added in line The method is injected into the cellulose spinning solution, specifically, an online adding device for calamine mother liquor is installed on the cellulose spinning solution delivery pipeline on the production line, wherein the mass ratio of the cellulose spinning solution to the calamine mother liquor is 3- 20:1. 7. the preparation method of cellulose/calamine composite fiber according to claim 1 is characterized in that, the technology that functional spinning liquid prepares cellulose/calamine composite fiber is wet spinning process or dry spraying wet spinning process. 8. the cellulose/calamine composite fiber that the preparation method of cellulose/calamine composite fiber as claimed in claim 1 makes, is characterized in that: described cellulose/calamine composite fiber monofilament fineness is 0.9-4.8dtex, the dry breaking strength is 1.7-4.5cN/dtex.