CN112127009A - Cellulose/calcium alginate blend fiber with skin-core structure and preparation method thereof - Google Patents
Cellulose/calcium alginate blend fiber with skin-core structure and preparation method thereof Download PDFInfo
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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Abstract
The invention provides a skin-core structure cellulose/calcium alginate blend fiber and a preparation method thereof, the method comprises the steps of respectively feeding a cellulose solution I and a cellulose/alginic acid blend solution into a skin-core composite spinning component, extruding the mixture through a spinneret orifice, sequentially entering an air section, a first coagulation bath and a second coagulation bath, and then washing and drying the mixture to prepare the skin-core structure cellulose/calcium alginate blend fiber; wherein the viscosity ratio of the cellulose solution I flowing through the skin layer channel to the cellulose/alginic acid blending solution flowing through the core layer channel is 1: 0.9-1.1; the prepared skin-core structure cellulose/calcium alginate blend fiber comprises a cellulose component and a calcium alginate component dispersed in the cellulose component; and the content of calcium alginate is gradually increased from the core layer to the cortex layer; the mass loss rate of alginic acid in the forming process is 3-10%; the limiting oxygen index of the skin-core structure cellulose/calcium alginate blend fiber is 27-30%, and the self-extinguishing time after leaving fire is 3-5 s.
Description
Technical Field
The invention belongs to the technical field of biomass regenerated fibers, and relates to a skin-core structure cellulose/calcium alginate blend fiber and a preparation method thereof.
Background
The regenerated cellulose fiber is a chemical fiber prepared by wet spinning by using cellulose as a raw material. The regenerated cellulose fiber has the advantages of resource sustainability, good wearing comfort, degradability and the like, and is an indispensable fiber material. However, regenerated cellulose fibers suffer from the disadvantage of being flammable. In order to improve the comprehensive performance of the regenerated cellulose fiber, the flame-retardant regenerated cellulose fiber can be prepared by methods such as after-treatment, solution addition and the like. The problem of insufficient washing fastness exists in the preparation of the flame-retardant regenerated cellulose fiber by a post-finishing method. The flame-retardant regenerated cellulose fiber prepared by the solution addition method has large addition amount of the flame retardant, poor compatibility with cellulose and greatly reduced mechanical strength.
Alginic acid such as alginic acid, sodium alginate, calcium alginate and the like and metal salts thereof are another natural polymer with huge yield. Alginic acid and calcium alginate are insoluble in water, and sodium alginate is easily soluble in water. The calcium alginate fiber can be prepared by adopting a sodium alginate solution and a calcium chloride solution as a coagulating bath through a wet spinning method. The calcium alginate fiber has excellent flame retardant property, the limiting oxygen index reaches 34.4 percent, and belongs to the flame-retardant fiber (the structure and the performance of the calcium alginate fiber [ J ]. the synthetic fiber industry, 2009(06): 5-8.). The calcium alginate fibers have the problems of low mechanical properties and poor chemical resistance stability, and are not suitable for taking.
Cellulose and alginic acid both belong to natural high molecular polysaccharide, and the cellulose and the alginic acid are mixed to prepare cellulose/calcium alginate composite fibers or blended fibers. Seacell alginate fiber produced by Smartfiber company of Germany is prepared by adding fine particles of natural seaweed containing calcium alginate into cellulose/NMMO spinning solution, and spinning by dry-jet wet method to obtain Lyocell fiber containing calcium alginate. Chinese patent ZL 201610848098.5 (a preparation method of cellulose/calcium alginate blend fiber) is to add sodium alginate and calcium chloride into cellulose/NMMO spinning solution to prepare cellulose/calcium alginate blend fiber with mass fraction less than 5%. The cellulose/calcium alginate fiber prepared by the two methods has low content of calcium alginate, can not prevent the combustion of cellulose, and has no flame retardant property.
Therefore, the research on the cellulose/calcium alginate blend fiber with good mechanical property and flame retardant property is of great significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a cellulose/calcium alginate blend fiber with a skin-core structure and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of a skin-core structure cellulose/calcium alginate blend fiber comprises the following steps: respectively feeding a cellulose solution I and a cellulose/alginic acid blended solution to a skin-core composite spinning assembly, wherein the cellulose solution I enters a skin layer channel, the cellulose/alginic acid blended solution enters a core layer channel, the cellulose/alginic acid blended solution enters an air section, a first coagulation bath and a second coagulation bath after being extruded through a spinneret orifice, and the cellulose/calcium alginate blended fiber with the skin-core structure is prepared after water washing and drying;
the viscosity ratio of the cellulose solution I flowing through the skin layer channel to the cellulose/alginic acid blending solution flowing through the core layer channel is 1: 0.9-1.1.
As a preferred technical scheme:
according to the preparation method of the skin-core structure cellulose/calcium alginate blend fiber, the cellulose solution I is prepared by dissolving cellulose in ionic liquid; the mass fraction of cellulose in the cellulose solution I is 4-10%, and the mass fraction of the ionic liquid is 90-96%;
the cellulose/alginic acid blending solution is prepared by mixing a cellulose solution II and an alginic acid solution, wherein the cellulose solution II is prepared by dissolving cellulose in an ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in the ionic liquid, and the viscosity ratio of the cellulose solution II to the alginic acid solution is 500-1000: 1;
the mass fraction of cellulose in the cellulose/alginic acid blending solution is 6-12%, the mass ratio of cellulose to alginic acid is 3-1: 1, and the mass fraction of the ionic liquid is 83.5-90%;
the first coagulation bath is an aqueous ionic liquid solution.
According to the preparation method of the cellulose/calcium alginate blend fiber with the skin-core structure, the polymerization degree of the cellulose in the cellulose/alginic acid blend solution is 100-200 lower than that of the cellulose in the cellulose solution I.
According to the preparation method of the cellulose/calcium alginate blend fiber with the skin-core structure, the polymerization degree of cellulose in the cellulose/alginic acid blend solution is 300-600, and the polymerization degree of cellulose in the cellulose solution I is 400-800.
According to the preparation method of the skin-core structure cellulose/calcium alginate blend fiber, the length of the air section is 3-10 mm, and the temperature is 5-25 ℃. (air space length, temperature, mainly to orient the high molecules in solution, have an effect on the degree of orientation and crystallinity of the fibers).
According to the preparation method of the skin-core structure cellulose/calcium alginate blend fiber, the mass fraction of the ionic liquid aqueous solution is 0-10%, and (when water is used as a main component in the solution, the ionic liquid does not have the capacity of dissolving cellulose, because the interaction between the water and the ionic liquid is stronger than that between the cellulose and the ionic liquid, the ionic liquid in the cellulose solution can enter the aqueous solution, namely double diffusion), the temperature of the first coagulation bath is 5-15 ℃, the drawing ratio of the fiber in the first coagulation bath is 4-7 times, and the retention time is 3-6 s;
the second coagulation bath is a calcium chloride water solution with the mass fraction of 1-5%, the temperature of the second coagulation bath is 5-15 ℃, the drawing ratio of the fiber in the second coagulation bath is 1-2 times, and the retention time is 2-5 s.
In the preparation method of the skin-core structure cellulose/calcium alginate blend fiber, the ionic liquid is 1-allyl-3-methylimidazole chloride salt or 1-butyl-3-methylimidazole acetate.
The invention also provides the skin-core structure cellulose/calcium alginate blend fiber prepared by the method: the skin-core structure cellulose/calcium alginate blend fiber mainly comprises a cellulose component and a calcium alginate component dispersed in the cellulose component;
the cellulose component consists of a skin layer cellulose component and a core layer cellulose component, and hydrogen bond interaction exists at the interface of the skin layer cellulose component and the core layer cellulose component; the alginic acid is crosslinked by divalent metal calcium ions to form calcium alginate without water solubility;
the mass ratio of the skin layer to the core layer is 1: 1-2 (wherein the skin layer refers to the mass sum of the cellulose component and the calcium alginate component in the skin layer, the core layer refers to the mass sum of the cellulose component and the calcium alginate component in the core layer), the content of the calcium alginate dispersed in the cellulose component of the core layer is lower than that of the calcium alginate dispersed in the cellulose component of the skin layer, the content of the calcium alginate gradually increases from the core layer to the skin layer, and the content of the calcium alginate in the core layer accounts for 30-45% of the total mass of the calcium alginate in the fiber.
The mass ratio of the skin layer of the cellulose/calcium alginate blend fiber prepared by the invention is less than or equal to that of the core layer, and the calcium alginate is mainly present in the skin layer cellulose. Because the skin layer contains a certain amount of calcium alginate, the fiber has flame retardant property, and the content of calcium alginate in the inner core layer is not required.
As a preferred technical scheme:
according to the skin-core structure cellulose/calcium alginate blend fiber, the crystallinity of the cellulose component of the core layer is 45-65%, and the orientation degree is 75-85%; the crystallinity of the cortical cellulose component is 46-67%, and the orientation degree is 73-88%.
The cellulose/calcium alginate blended fiber takes cellulose as a continuous phase, so that the crystallization and orientation degree of the cellulose are closely related to the properties of the fiber, such as breaking strength and the like. The crystallization and the orientation degree are in positive correlation with the cellulose concentration, the polymerization degree, the cellulose/alginic acid/component ratio and the air section drawing speed. According to the invention, the concentration of the core layer cellulose is higher than that of the skin layer cellulose, however, the polymerization degree of the skin layer cellulose is higher than that of the core layer cellulose, the skin layer cellulose solution does not contain alginic acid, and the cellulose orientation can be effectively induced in the air section solution stretching process, so that the interference of alginic acid is avoided. Combining the effects of the above factors, the crystallinity and orientation degree of the sheath cellulose fiber and the core cellulose fiber are similar.
The sheath-core structure cellulose/calcium alginate blend fiber has the fineness of 2.5-4.5 dtex (measured according to GB/T14335), the dry state breaking strength of 2.5-3.5 cN/dtex, the wet state breaking strength of 1.9-2.9 cN/dtex, the dry state breaking elongation of 7-11% (the dry state breaking strength, the wet state breaking strength and the dry state breaking elongation are measured according to GB/T14337), and the standard moisture regain of 11-16% (measured according to GB/T6503);
the mass loss rate of alginic acid in the forming process (the process specifically refers to the process from the bi-component spinning assembly to the washing and drying process) is 3-10%; the limiting oxygen index of the skin-core structure cellulose/calcium alginate blend fiber is 27-30%, and the self-extinguishing time after leaving fire is 3-5 s.
The mechanism of the invention is as follows:
the content of calcium alginate in the prepared blended fiber gradually increases from the fiber core layer to the skin layer and is distributed in a gradient manner. And the calcium alginate content in the cortex is high, so that a better flame retardant effect can be achieved. Compared with the blended fiber containing the same calcium alginate content, the fiber with the sheath-core layer structure prepared by the invention has better flame retardant effect. The dispersion of calcium alginate is mainly realized by skin-core composite spinning, double diffusion in the solidification process and regulation and control of the concentration and polymerization degree of cellulose in the spinning solution.
In order to achieve the purpose, the invention adopts a skin-core composite spinning method, a core layer solution is a cellulose/alginic acid blended solution, a skin layer solution is a cellulose solution I, and two coagulating baths are arranged, wherein the first coagulating bath is an ionic liquid aqueous solution coagulating bath, and the second coagulating bath is a calcium chloride solution coagulating bath. And extruding the spinning solution through a spinning assembly to form a spinning stream, and allowing the spinning stream to enter a first coagulation bath to carry out double diffusion of a solvent (ionic liquid) and a non-solvent (water). The reason of double diffusion is concentration gradient, and the ionic liquid content in the spinning trickle (namely the spinning solution of the skin layer and the core layer) is 83.5-96%; in the first coagulation bath, the content of the ionic liquid is 0-10%. Therefore, after the spinning fine flow enters the first coagulation bath, the ionic liquid content in the spinning fine flow is high, and the water content is low. While the first coagulation bath has a low ionic liquid content and a high water content. The ionic liquid in the spinning plume diffuses toward the first coagulation bath, while the water in the first coagulation bath diffuses toward the spinning plume. In addition, the mass of the spinning stream is only a very small proportion of the total mass of the first coagulation bath, and in the coagulation bath with the ionic liquid content of 0-10%, cellulose is coagulated and formed, but is not continuously in a solution state. The cellulose solution I of the skin layer is firstly solidified, and the solidification time point of the cellulose/alginic acid blending solution of the core layer is later than that of the cellulose solution I of the skin layer. Therefore, the contact time of the alginic acid and the coagulation bath is later than that of the cortical cellulose, and the alginic acid cannot be quickly contacted with the coagulation bath and run off. The second coagulating bath is calcium chloride solution, and divalent metal calcium ions can be crosslinked with alginic acid to convert the divalent metal calcium ions into water-insoluble calcium alginate with flame retardant property. Since the solvent ionic liquid mainly enters the first coagulation bath, the amount of solvent entering the second coagulation bath is small (because the spinning stream enters the first coagulation bath, double diffusion occurs, the ionic liquid in the spinning stream mainly enters the first coagulation bath, and the fiber entering the second coagulation bath is mainly cellulose and water and contains a small part of ionic liquid, so that the amount of ionic liquid in the second coagulation bath is small). The cost of recovery of the solvent in the coagulation bath is an important component part of the cost of fiber production. The first coagulation bath contained only ionic liquid and water, and no calcium chloride. Therefore, only the ionic liquid and water need to be separated in the recovery process, and compared with an ionic liquid aqueous solution containing calcium chloride, the ionic liquid aqueous solution has low requirements on the recovery process and low solvent ionic liquid recovery cost.
Spinning flows out of a spinneret orifice, alginic acid exists in a core layer blending solution before entering a coagulation bath, cellulose in the blending solution is a main component and is a continuous phase, and alginic acid is a dispersed phase, and in order to realize gradient distribution of alginic acid in the final fiber, the invention adopts the technology and the principle that: in the blending solution, the viscosity ratio of the cellulose solution II to the alginic acid solution is 500-1000: 1, the ionic liquid enters a coagulating bath, and the alginic acid solution is low in viscosity and easy to flow, and can move along the outside of the fiber along with the solvent and enter the cortical layer cellulose. The double diffusion rate is shown below, and a concentration gradient of the solvent can control the diffusion rate.
The diffusion rate v of the solvent in the coagulation bath is defined as:
in the formula: d-diffusion coefficient (cm)2/s)；
A-area (cm) through which the diffuser passes2)；
Lambda m-the amount of diffusing matter (g);
Λ t-diffusion time(s);
because alginic acid has low viscosity and the solidification process flows along with the solvent, the quantity of dispersed substance (g), which is ^ m in the formula, can be approximately understood as the quantity of alginic acid moving, and the formula is rewritten as:
according to the formula, the influencing factors influencing the alginic acid movement comprise diffusion coefficient, area through which the diffuser passes, concentration gradient and diffusion time. Assuming a constant area is traversed by the diffuser, factors influencing the motion of alginic acid include:
1) the diffusion coefficient is temperature dependent in the case of a constant composition, and the higher the temperature, the faster the diffusion, and the higher the diffusion coefficient. Therefore, the temperature of the coagulating bath is increased, the diffusion is accelerated, the outward migration of alginic acid can be promoted, and the amount of alginic acid entering the core layer from the skin layer is increased. Reducing the temperature, so that the moving amount of the alginic acid is reduced;
2) the concentration gradient, i.e. the first coagulation bath concentration (the content of ionic liquid in the coagulation bath), was adjusted. Under the premise that the ionic liquid content in the spinning solution is fixed, the ionic liquid content of the coagulating bath is increased, which means that the concentration gradient is reduced, and the speed of the ionic liquid in the spinning solution entering the coagulating bath is slowed down. Alginic acid has low viscosity and flows with the solvent ionic liquid, and the flow driving force and the flow distance along the radial direction of the fiber of alginic acid are reduced under the condition of small concentration gradient. Similarly, the concentration gradient is increased, which can promote the flow of alginic acid (the solvent is fiber-yielding, so the solvent moves along the radial direction of the fiber, and the alginic acid moves along the radial direction of the fiber);
3) diffusion time, the longer the diffusion time, i.e. the longer the time the fiber is in the coagulation bath, the greater the amount of outward migration of alginic acid.
The first coagulation bath adopted by the invention is an ionic liquid aqueous solution, and the mass fraction of the ionic liquid, the coagulation bath temperature, the spinning solution composition and other parameters are matched, so that the alginic acid is ensured to enter the cortex, and the calcium alginate content is gradually increased from the fiber core layer to the cortex and is distributed in a gradient manner.
In order to realize the effect of calcium alginate gradient distribution, the parameter design of the spinning solution is also needed to be combined. Because alginic acid has a very low viscosity, it has little effect on the viscosity of the blending solution. Thus, the degree of polymerization and the concentration of cellulose are the main factors affecting the viscosity of the solution. The viscosity of the cellulose solution I is higher than that of the cellulose/alginic acid blending solution under the condition of the same content of cellulose. In order to ensure that the viscosities of the cortical layer cellulose solution I and the core layer cellulose/alginic acid blended solution are equal, the invention utilizes the characteristic that the concentration and the polymerization degree of the cellulose solution are in positive correlation with the solution viscosity, and the viscosities of the cellulose solution I and the cellulose/alginic acid blended solution are close to each other by adjusting the cellulose content and the cellulose polymerization degree in the solution, namely the concentration of the cellulose solution I is less than that of the cellulose in the cellulose/alginic acid blended solution, and the polymerization degree of the cellulose in the cellulose solution I is higher than that of the cellulose in the cellulose/alginic acid blended solution. When the viscosity of the core layer cellulose/alginic acid blending solution is similar to that of the skin layer cellulose solution I, the inconsistency of stretching tension borne by an air section stretching process can be avoided, the core layer cellulose/alginic acid blending solution can be synchronously stretched under the tension action, and the high polymer solution has viscoelasticity, and is stretched just because of the viscoelasticity.
The cellulose in the cellulose/calcium alginate blend fiber is a continuous phase, the higher the content of the cellulose is, the more compact the fiber structure is, and the lower the content of the cellulose is, the more loose the fiber structure is. The concentration of the cellulose solution I is lower than that of cellulose in the cellulose/alginic acid blending solution, and the compactness of the cellulose of the skin layer is lower than that of the cellulose of the core layer. Because the cellulose structure of the cortex is relatively loose, calcium alginate is easier to enter, and a dispersed state with the calcium alginate content of the cortex higher than that of the calcium alginate content of the core layer is formed.
Advantageous effects
(1) The invention adopts a two-step coagulation bath design, the first coagulation bath is aqueous solution and the second coagulation bath is calcium chloride solution, and the first coagulation bath only contains ionic liquid and water, so that the difficulty of solvent purification is reduced;
(2) the cellulose/alginic acid blend fiber has low alginic acid loss rate in the forming and using processes, and calcium alginate is distributed in a gradient manner and is enriched in the cortex of the fiber, so that the fiber has good flame retardant property and reaches the standard of flame retardant fiber;
(3) the cellulose/alginic acid blend fiber produced by the invention has high calcium alginate content and higher mechanical property, and solves the negative influence on the mechanical property of the fiber caused by the increase of the calcium alginate content to a certain extent.
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.
The types of ionic liquids in the specific examples are shown in table 1.
Example 1
A preparation method of cellulose/alginic acid blend fiber comprises the steps of taking a cellulose solution I as a skin component and a cellulose/alginic acid blend solution as a core component, spinning by adopting a skin-core composite spinning method, sequentially entering an air section, a first coagulation bath (5% by mass of an ionic liquid aqueous solution) and a second coagulation bath (1% by mass of a calcium chloride aqueous solution), washing with water, and drying to obtain the cellulose/alginic acid blend fiber;
the cellulose solution I is prepared by dissolving cellulose with the polymerization degree of 400 in an ionic liquid, the cellulose/alginic acid blending solution is prepared by mixing a cellulose solution and an alginic acid solution, the cellulose solution is prepared by dissolving cellulose with the polymerization degree of 300 in the ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in the ionic liquid, and the viscosity ratio of the cellulose solution to the alginic acid solution is 600: 1; in the cellulose solution I, the mass fraction of cellulose is 10%, and the mass fraction of ionic liquid is 90%; in the cellulose/alginic acid blending solution, the mass fraction of cellulose is 12 percent, and the mass fraction of ionic liquid is 84 percent; the mass ratio of the cellulose to the alginic acid is 3: 1; the viscosity ratio of the cellulose solution I to the cellulose/alginic acid blending solution is 1: 1.05; the length of the air section is 4mm, and the temperature is 5 ℃; the temperature of the first coagulating bath is 5 ℃, the drawing ratio of the fiber in the first coagulating bath is 7 times, and the retention time is 3 s; the temperature of the second coagulation bath was 10 ℃, the draw ratio of the fiber in the second coagulation bath was 1 time, and the residence time was 2 seconds.
The finally prepared cellulose/alginic acid blend fiber comprises a cellulose component and calcium alginate, wherein the content of the calcium alginate is gradually increased from a fiber core layer to a skin layer and is distributed in a gradient manner, the mass ratio of the skin layer to the core layer is 1:1, and the content of the calcium alginate in the core layer accounts for 30% of the total mass of the calcium alginate in the fiber; the cellulose component in the core layer of the fiber had a crystallinity of 65% and an orientation of 85%. The cellulose component in the fiber sheath layer had a crystallinity of 67% and an orientation of 88%; the titer of the cellulose/alginic acid blended fiber is 4dtex, the dry breaking strength is 3.5cN/dtex, the wet breaking strength is 2.9cN/dtex, the dry breaking elongation is 8 percent, and the standard moisture regain is 11 percent; the alginic acid was lost at 3% during the forming process. The limiting oxygen index of the blended fiber is 30%, and the self-extinguishing time from fire is 5 s.
Comparative example 1
A method for preparing cellulose/calcium alginate blend fiber, which is substantially the same as that in example 1, except that the spinning method adopted is extrusion of a conventional monocomponent spinning assembly, the loss rate of alginic acid in the forming process is 90%, the limiting oxygen index of the fiber is 20%, and the fiber is not self-extinguished after being left from a fire. Comparing example 1 with comparative example 1, it can be seen that, using the conventional monocomponent dry-jet wet spinning method, alginic acid in a 90% mass fraction of the blended solution enters the coagulation bath, and the amount of alginic acid present in the fiber is very small because the conventional spinning cannot prevent alginic acid from entering the coagulation bath with the solvent ionic liquid.
Comparative example 2
The preparation method of the cellulose/alginic acid blended fiber is basically the same as that of the fiber in example 1, except that the polymerization degrees of the cellulose I and the cellulose II are the same and are both 300.
In the finally prepared cellulose/alginic acid blended fiber, the crystallinity of the cellulose II component in the fiber core layer is 63 percent, the orientation degree is 80 percent, the crystallinity of the cellulose I component in the fiber skin layer is 50 percent, and the orientation degree is 70 percent; the titer of the cellulose/alginic acid blended fiber is 4.0dtex, the dry fracture strength is 3.2cN/dtex, and the wet fracture strength is 2.3 cN/dtex; the alginic acid was lost at 15% during the forming process, and the limiting oxygen index of the blended fiber was 24%. Comparing example 1 with comparative example 2, it can be seen that the fiber mechanical property of comparative example 1 is deteriorated, and alginic acid loss rate is increased because the degree of polymerization of the sheath layer cellulose I is the same as that of the core layer cellulose II, so that the viscosity of the sheath layer cellulose solution I is lower than that of the core layer cellulose blending solution, and the effect of stretching on the orientation of the core layer cellulose II is stronger than that of the sheath layer cellulose I. Therefore, the degree of orientation of the cellulose II in the skin layer becomes small, the crystallinity is reduced, and the mechanical properties of the fiber as a whole are low. The excessive viscosity difference also enables the cortex solution and the core layer solution to be mixed in the composite process, and the alginic acid solution enters the cortex cellulose II solution before entering the coagulation bath, so that the alginic acid loss rate is high.
Example 2
A preparation method of cellulose/alginic acid blend fiber comprises the steps of taking a cellulose solution I as a skin component and a cellulose/alginic acid blend solution as a core component, spinning by adopting a skin-core composite spinning method, sequentially entering an air section, a first coagulation bath (water) and a second coagulation bath (calcium chloride aqueous solution with the mass fraction of 1%), washing with water, and drying to obtain the cellulose/alginic acid blend fiber;
the cellulose solution I is prepared by dissolving cellulose with the polymerization degree of 500 in an ionic liquid, the cellulose/alginic acid blending solution is prepared by mixing a cellulose solution and an alginic acid solution, the cellulose solution is prepared by dissolving cellulose with the polymerization degree of 400 in the ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in the ionic liquid, and the viscosity ratio of the cellulose solution to the alginic acid solution is 700: 1; in the cellulose solution I, the mass fraction of cellulose is 9%, and the mass fraction of ionic liquid is 91%; in the cellulose/alginic acid blending solution, the mass fraction of cellulose is 11%, and the mass fraction of ionic liquid is 83.5%; the mass ratio of the cellulose to the alginic acid is 2: 1; the viscosity ratio of the cellulose solution I to the cellulose/alginic acid blending solution is 1: 0.9; the length of the air section is 7mm, and the temperature is 8 ℃; the temperature of the first coagulating bath is 7 ℃, the drawing ratio of the fiber in the first coagulating bath is 6 times, and the retention time is 3 s; the temperature of the second coagulation bath was 7 ℃, the draw ratio of the fiber in the second coagulation bath was 1 time, and the residence time was 3 seconds.
The finally prepared cellulose/alginic acid blend fiber comprises a cellulose component and calcium alginate, wherein the content of the calcium alginate is gradually increased from the core layer of the fiber to the skin layer and is distributed in a gradient manner, the mass ratio of the skin layer to the core layer is 1:1.2, and the content of the calcium alginate in the core layer accounts for 33 percent of the total mass of the calcium alginate in the fiber; the cellulose component in the core layer of the fiber had a crystallinity of 60% and an orientation of 83%. The crystallinity of the cellulose component in the fiber sheath layer is 63%, and the orientation degree is 81%; the titer of the cellulose/alginic acid blended fiber is 4.5dtex, the dry breaking strength is 2.9cN/dtex, the wet breaking strength is 2.1cN/dtex, the dry breaking elongation is 9%, and the standard moisture regain is 13%; the alginic acid was lost at 4% during the forming process. The limiting oxygen index of the blended fiber is 29 percent, and the self-extinguishing time from fire is 5 s.
Example 3
A preparation method of cellulose/alginic acid blend fiber comprises the steps of taking a cellulose solution I as a skin component and a cellulose/alginic acid blend solution as a core component, spinning by adopting a skin-core composite spinning method, sequentially entering an air section, a first coagulation bath (an ionic liquid aqueous solution with the mass concentration of 6%) and a second coagulation bath (a calcium chloride aqueous solution with the mass fraction of 2%), washing with water, and drying to obtain the cellulose/alginic acid blend fiber;
the cellulose solution I is prepared by dissolving cellulose with the polymerization degree of 600 in ionic liquid, the cellulose/alginic acid blending solution is prepared by mixing cellulose solution and alginic acid solution, the cellulose solution is prepared by dissolving cellulose with the polymerization degree of 450 in ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in ionic liquid, and the viscosity ratio of the cellulose solution to the alginic acid solution is 800: 1; in the cellulose solution I, the mass fraction of cellulose is 8%, and the mass fraction of ionic liquid is 92%; in the cellulose/alginic acid blending solution, the mass fraction of cellulose is 10 percent, and the mass fraction of ionic liquid is 86 percent; the mass ratio of the cellulose to the alginic acid is 2.5: 1; the viscosity ratio of the cellulose solution I to the cellulose/alginic acid blending solution is 1: 1.1; the length of the air section is 5mm, and the temperature is 10 ℃; the temperature of the first coagulating bath is 11 ℃, the drawing ratio of the fiber in the first coagulating bath is 4 times, and the retention time is 4 s; the temperature of the second coagulation bath was 12 ℃, the draw ratio of the fiber in the second coagulation bath was 2 times, and the residence time was 4 seconds.
The finally prepared cellulose/alginic acid blend fiber comprises a cellulose component and calcium alginate, wherein the content of the calcium alginate is gradually increased from the core layer of the fiber to the skin layer and is distributed in a gradient manner, the mass ratio of the skin layer to the core layer is 1:1.4, and the content of the calcium alginate in the core layer accounts for 35 percent of the total mass of the calcium alginate in the fiber; the cellulose component in the core layer of the fiber had a crystallinity of 55% and an orientation of 82%. The cellulose component in the fiber sheath layer had a crystallinity of 54% and an orientation of 84%; the titer of the cellulose/alginic acid blended fiber is 3.4dtex, the dry breaking strength is 2.7cN/dtex, the wet breaking strength is 2cN/dtex, the dry breaking elongation is 7%, and the standard moisture regain is 14%; the alginic acid was lost at 5% during the forming process. The limiting oxygen index of the blended fiber is 29 percent, and the self-extinguishing time from fire is 4 s.
Example 4
A preparation method of cellulose/alginic acid blend fiber comprises the steps of taking a cellulose solution I as a skin component and a cellulose/alginic acid blend solution as a core component, spinning by adopting a skin-core composite spinning method, sequentially entering an air section, a first coagulation bath (an ionic liquid aqueous solution with the mass concentration of 3%) and a second coagulation bath (a calcium chloride aqueous solution with the mass concentration of 3%), washing with water, and drying to obtain the cellulose/alginic acid blend fiber;
the cellulose solution I is prepared by dissolving cellulose with the polymerization degree of 550 in an ionic liquid, the cellulose/alginic acid blending solution is prepared by mixing a cellulose solution and an alginic acid solution, the cellulose solution is prepared by dissolving cellulose with the polymerization degree of 400 in the ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in the ionic liquid, and the viscosity ratio of the cellulose solution to the alginic acid solution is 700: 1; in the cellulose solution I, the mass fraction of cellulose is 6%, and the mass fraction of ionic liquid is 94%; in the cellulose/alginic acid blending solution, the mass fraction of cellulose is 9 percent, and the mass fraction of ionic liquid is 87.4 percent; the mass ratio of the cellulose to the alginic acid is 2.5: 1; the viscosity ratio of the cellulose solution I to the cellulose/alginic acid blending solution is 1: 0.95; the length of the air section is 4mm, and the temperature is 13 ℃; the temperature of the first coagulating bath is 15 ℃, the drawing ratio of the fiber in the first coagulating bath is 5 times, and the retention time is 4 s; the temperature of the second coagulation bath was 15 ℃, the draw ratio of the fiber in the second coagulation bath was 1.5 times, and the residence time was 2 seconds.
The finally prepared cellulose/alginic acid blend fiber comprises a cellulose component and calcium alginate, wherein the content of the calcium alginate is gradually increased from the core layer of the fiber to the skin layer and is distributed in a gradient manner, the mass ratio of the skin layer to the core layer is 1:1.5, and the content of the calcium alginate in the core layer accounts for 37 percent of the total mass of the calcium alginate in the fiber; the cellulose component in the core layer of the fiber had a crystallinity of 58% and an orientation of 80%. The crystallinity of the cellulose component in the fiber sheath layer is 60%, and the orientation degree is 81%; the titer of the cellulose/alginic acid blended fiber is 2.9dtex, the dry breaking strength is 3.1cN/dtex, the wet breaking strength is 2.4cN/dtex, the dry breaking elongation is 9%, and the standard moisture regain is 15%; the alginic acid was lost at 7% during the forming process. The limiting oxygen index of the blended fiber was 28% and the time to self-extinguish from fire was 4 s.
Example 5
A preparation method of cellulose/alginic acid blend fiber comprises the steps of taking a cellulose solution I as a skin component and a cellulose/alginic acid blend solution as a core component, spinning by adopting a skin-core composite spinning method, sequentially entering an air section, a first coagulation bath (4% by mass of an ionic liquid aqueous solution) and a second coagulation bath (3% by mass of a calcium chloride aqueous solution), washing with water, and drying to obtain the cellulose/alginic acid blend fiber;
the cellulose solution I is prepared by dissolving cellulose with the polymerization degree of 550 in an ionic liquid, the cellulose/alginic acid blending solution is prepared by mixing a cellulose solution and an alginic acid solution, the cellulose solution is prepared by dissolving cellulose with the polymerization degree of 500 in the ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in the ionic liquid, and the viscosity ratio of the cellulose solution to the alginic acid solution is 900: 1; in the cellulose solution I, the mass fraction of cellulose is 6%, and the mass fraction of ionic liquid is 94%; in the cellulose/alginic acid blending solution, the mass fraction of cellulose is 7 percent, and the mass fraction of ionic liquid is 89.5 percent; the mass ratio of the cellulose to the alginic acid is 2: 1; the viscosity ratio of the cellulose solution I to the cellulose/alginic acid blending solution is 1: 0.97; the length of the air section is 7mm, and the temperature is 20 ℃; the temperature of the first coagulating bath is 13 ℃, the drawing ratio of the fiber in the first coagulating bath is 6 times, and the retention time is 5 s; the temperature of the second coagulation bath was 6 ℃, the draw ratio of the fiber in the second coagulation bath was 1 time, and the residence time was 2 seconds.
The finally prepared cellulose/alginic acid blend fiber comprises a cellulose component and calcium alginate, wherein the content of the calcium alginate is gradually increased from the core layer of the fiber to the skin layer and is distributed in a gradient manner, the mass ratio of the skin layer to the core layer is 1:1.6, and the content of the calcium alginate in the core layer accounts for 39% of the total mass of the calcium alginate in the fiber; the cellulose component in the core layer of the fiber had a crystallinity of 57% and an orientation of 79%. The crystallinity of the cellulose component in the fiber sheath layer is 59%, and the orientation degree is 80%; the titer of the cellulose/alginic acid blended fiber is 2.5dtex, the dry breaking strength is 2.9cN/dtex, the wet breaking strength is 2.3cN/dtex, the dry breaking elongation is 11%, and the standard moisture regain is 15%; the alginic acid was lost at 7% during the forming process. The limiting oxygen index of the blended fiber was 28% and the self-extinguishing time from fire was 3 s.
Example 6
A preparation method of cellulose/alginic acid blend fiber comprises the steps of taking a cellulose solution I as a skin component and a cellulose/alginic acid blend solution as a core component, spinning by adopting a skin-core composite spinning method, sequentially entering an air section, a first coagulation bath (an ionic liquid aqueous solution with the mass concentration of 8%) and a second coagulation bath (a calcium chloride aqueous solution with the mass fraction of 4%), washing with water, and drying to obtain the cellulose/alginic acid blend fiber;
the cellulose solution I is prepared by dissolving cellulose with the polymerization degree of 600 in ionic liquid, the cellulose/alginic acid blending solution is prepared by mixing cellulose solution and alginic acid solution, the cellulose solution is prepared by dissolving cellulose with the polymerization degree of 500 in ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in ionic liquid, and the viscosity ratio of the cellulose solution to the alginic acid solution is 850: 1; in the cellulose solution I, the mass fraction of cellulose is 5%, and the mass fraction of ionic liquid is 95%; in the cellulose/alginic acid blending solution, the mass fraction of cellulose is 6 percent, and the mass fraction of ionic liquid is 90 percent; the mass ratio of the cellulose to the alginic acid is 1.5: 1; the viscosity ratio of the cellulose solution I to the cellulose/alginic acid blending solution is 1: 1.01; the length of the air section is 3mm, and the temperature is 25 ℃; the temperature of the first coagulating bath is 8 ℃, the drawing ratio of the fiber in the first coagulating bath is 4 times, and the retention time is 4 s; the temperature of the second coagulation bath was 5 ℃, the draw ratio of the fiber in the second coagulation bath was 2 times, and the residence time was 5 seconds.
The finally prepared cellulose/alginic acid blend fiber comprises a cellulose component and calcium alginate, wherein the content of the calcium alginate is gradually increased from the core layer of the fiber to the skin layer and is distributed in a gradient manner, the mass ratio of the skin layer to the core layer is 1:1.8, and the content of the calcium alginate in the core layer accounts for 42 percent of the total mass of the calcium alginate in the fiber; the cellulose component in the core layer of the fiber had a crystallinity of 50% and an orientation of 77%. The crystallinity of the cellulose component in the fiber sheath layer was 51%, and the degree of orientation was 79%; the titer of the cellulose/alginic acid blended fiber is 3.1dtex, the dry breaking strength is 3cN/dtex, the wet breaking strength is 2.4cN/dtex, the dry breaking elongation is 10%, and the standard moisture regain is 16%; the alginic acid was lost at 8% during the forming process. The limiting oxygen index of the blended fiber was 27% and the self-extinguishing time from fire was 3 s.
Example 7
A preparation method of cellulose/alginic acid blend fiber comprises the steps of taking a cellulose solution I as a skin component and a cellulose/alginic acid blend solution as a core component, spinning by adopting a skin-core composite spinning method, sequentially entering an air section, a first coagulation bath (10% by mass of an ionic liquid aqueous solution) and a second coagulation bath (5% by mass of a calcium chloride aqueous solution), washing with water, and drying to obtain the cellulose/alginic acid blend fiber;
the cellulose solution I is prepared by dissolving cellulose with the polymerization degree of 800 in an ionic liquid, the cellulose/alginic acid blending solution is prepared by mixing a cellulose solution and an alginic acid solution, the cellulose solution is prepared by dissolving cellulose with the polymerization degree of 600 in the ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in the ionic liquid, and the viscosity ratio of the cellulose solution to the alginic acid solution is 1000: 1; in the cellulose solution I, the mass fraction of cellulose is 4%, and the mass fraction of ionic liquid is 96%; in the cellulose/alginic acid blending solution, the mass fraction of cellulose is 6 percent, and the mass fraction of ionic liquid is 88 percent; the mass ratio of the cellulose to the alginic acid is 1: 1; the viscosity ratio of the cellulose solution I to the cellulose/alginic acid blending solution is 1: 1; the length of the air section is 10mm, and the temperature is 13 ℃; the temperature of the first coagulating bath is 9 ℃, the drawing ratio of the fiber in the first coagulating bath is 5 times, and the retention time is 6 s; the temperature of the second coagulation bath was 9 ℃, the draw ratio of the fiber in the second coagulation bath was 1 time, and the residence time was 5 seconds.
The finally prepared cellulose/alginic acid blend fiber comprises a cellulose component and calcium alginate, wherein the content of the calcium alginate is gradually increased from the core layer of the fiber to the skin layer and is distributed in a gradient manner, the mass ratio of the skin layer to the core layer is 1:2, and the content of the calcium alginate in the core layer accounts for 45 percent of the total mass of the calcium alginate in the fiber; the cellulose component in the core layer of the fiber had a crystallinity of 45% and an orientation of 75%. The cellulose component in the fiber sheath layer had a crystallinity of 46% and an orientation of 73%; the titer of the cellulose/alginic acid blended fiber is 3.3dtex, the dry breaking strength is 2.5cN/dtex, the wet breaking strength is 1.9cN/dtex, the dry breaking elongation is 11%, and the standard moisture regain is 16%; the alginic acid was lost at 10% during the forming process. The limiting oxygen index of the blended fiber was 27% and the self-extinguishing time from fire was 3 s.
TABLE 1 kinds of ionic liquids corresponding to the respective examples
| Examples | Species of ionic liquids |
| Example 1 | 1-allyl-3-methylimidazolium chloride salt |
| Example 3 | 1-butyl-3-methylimidazolium acetate |
| Example 4 | 1-butyl-3-methylimidazolium acetate |
| Example 5 | 1-allyl-3-methylimidazolium chloride salt |
| Example 6 | 1-butyl-3-methylimidazolium acetate |
| Example 7 | 1-allyl-3-methylimidazolium chloride salt |
Claims (10)
1. A preparation method of cellulose/calcium alginate blend fiber with a skin-core structure is characterized by comprising the following steps: respectively feeding a cellulose solution I and a cellulose/alginic acid blended solution to a skin-core composite spinning assembly, wherein the cellulose solution I enters a skin layer channel, the cellulose/alginic acid blended solution enters a core layer channel, the cellulose/alginic acid blended solution enters an air section, a first coagulation bath and a second coagulation bath after being extruded through a spinneret orifice, and the cellulose/calcium alginate blended fiber with the skin-core structure is prepared after water washing and drying;
the viscosity ratio of the cellulose solution I flowing through the skin layer channel to the cellulose/alginic acid blending solution flowing through the core layer channel is 1: 0.9-1.1.
2. The method for preparing the skin-core structure cellulose/calcium alginate blend fiber according to claim 1, wherein the cellulose solution I is prepared by dissolving cellulose in ionic liquid; the mass fraction of cellulose in the cellulose solution I is 4-10%, and the mass fraction of the ionic liquid is 90-96%;
the cellulose/alginic acid blending solution is prepared by mixing a cellulose solution II and an alginic acid solution, wherein the cellulose solution II is prepared by dissolving cellulose in an ionic liquid, the alginic acid solution is prepared by dissolving alginic acid in the ionic liquid, and the viscosity ratio of the cellulose solution II to the alginic acid solution is 500-1000: 1;
the mass fraction of cellulose in the cellulose/alginic acid blending solution is 6-12%, the mass ratio of cellulose to alginic acid is 3-1: 1, and the mass fraction of the ionic liquid is 83.5-90%;
the first coagulation bath is an aqueous ionic liquid solution.
3. The method for preparing the skin-core structure cellulose/calcium alginate blend fiber according to claim 2, wherein the degree of polymerization of the cellulose in the cellulose/alginic acid blend solution is 100-200 lower than the degree of polymerization of the cellulose in the cellulose solution I.
4. The preparation method of the skin-core structure cellulose/calcium alginate blend fiber according to claim 3, wherein the degree of polymerization of the cellulose in the cellulose/alginic acid blend solution is 300-600, and the degree of polymerization of the cellulose in the cellulose solution I is 400-800.
5. The method for preparing the skin-core structure cellulose/calcium alginate blend fiber according to claim 4, wherein the length of the air section is 3-10 mm, and the temperature is 5-25 ℃.
6. The preparation method of the skin-core structure cellulose/calcium alginate blend fiber according to claim 5, wherein the mass fraction of the ionic liquid aqueous solution is 0-10%, the temperature of the first coagulation bath is 5-15 ℃, the drawing ratio of the fiber in the first coagulation bath is 4-7 times, and the retention time is 3-6 s;
the second coagulation bath is a calcium chloride water solution with the mass fraction of 1-5%, the temperature of the second coagulation bath is 5-15 ℃, the drawing ratio of the fiber in the second coagulation bath is 1-2 times, and the retention time is 2-5 s.
7. The method for preparing the skin-core structured cellulose/calcium alginate blend fiber according to claim 6, wherein the ionic liquid is 1-allyl-3-methylimidazole chloride salt or 1-butyl-3-methylimidazole acetate.
8. The skin-core structure cellulose/calcium alginate blend fiber prepared by the method of any one of claim 7, which is characterized in that: the skin-core structure cellulose/calcium alginate blend fiber mainly comprises a cellulose component and a calcium alginate component dispersed in the cellulose component;
the cellulose component consists of a skin layer cellulose component and a core layer cellulose component, and hydrogen bond interaction exists at the interface of the skin layer cellulose component and the core layer cellulose component;
the mass ratio of the skin layer to the core layer is 1: 1-2, the content of calcium alginate dispersed in the cellulose component of the core layer is lower than that of calcium alginate dispersed in the cellulose component of the skin layer, the content of calcium alginate gradually increases from the core layer to the skin layer, and the content of calcium alginate in the core layer accounts for 30-45% of the total mass of calcium alginate in the fiber.
9. The skin-core structure cellulose/calcium alginate blend fiber according to claim 8, wherein the cellulose component of the core layer has a crystallinity of 45-65% and an orientation of 75-85%; the crystallinity of the cortical cellulose component is 46-67%, and the orientation degree is 73-88%.
10. The skin-core structure cellulose/calcium alginate blend fiber according to claim 9, wherein the fineness of the skin-core structure cellulose/calcium alginate blend fiber is 2.5 to 4.5dtex, the dry breaking strength is 2.5 to 3.5cN/dtex, the wet breaking strength is 1.9 to 2.9cN/dtex, the dry elongation at break is 7 to 11%, and the standard moisture regain is 11 to 16%;
the mass loss rate of alginic acid in the forming process is 3-10%; the limiting oxygen index of the skin-core structure cellulose/calcium alginate blend fiber is 27-30%, and the self-extinguishing time after leaving fire is 3-5 s.
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