CN110804766A - Solvent method high wet modulus chitin fiber and preparation method thereof - Google Patents
Solvent method high wet modulus chitin fiber and preparation method thereof Download PDFInfo
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- CN110804766A CN110804766A CN201911300495.9A CN201911300495A CN110804766A CN 110804766 A CN110804766 A CN 110804766A CN 201911300495 A CN201911300495 A CN 201911300495A CN 110804766 A CN110804766 A CN 110804766A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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Abstract
The invention discloses a solvent method high wet modulus chitin fiber and a preparation method thereof, belonging to the field of textiles. The method comprises the following steps: (A) activating, namely activating the pulp by using cellulase to obtain pulp porridge; (B) squeezing, and squeezing and dehydrating the porridge to obtain water-containing cellulose; (C) pre-dissolving, namely mixing the water-containing cellulose, an N-methylmorpholine-N-oxide aqueous solution and a chitin aqueous solution to obtain pre-dissolved pulp; (D) dissolving, namely dissolving the pre-dissolved pulp in a dissolving machine to obtain pulp; (E) and spinning, namely spinning by adopting the slurry to obtain the solvent method high wet modulus chitin fiber. The method has the advantages of simple operation, no industrial pollution, low energy consumption, high safety performance and suitability for large-scale industrial continuous production. The prepared solvent method high wet modulus chitin fiber has high wet modulus, contains protein components, has good moisture absorption and sweat releasing performance and air permeability, is comfortable to wear, has soft hand feeling, is beneficial to continuous dyeing, is convenient to print and dye, and is beneficial to producing high-end fabrics.
Description
Technical Field
The invention relates to the technical field of spinning, in particular to a solvent method high wet modulus chitin fiber and a preparation method thereof.
Background
Regenerated cellulose fibers have evolved into two broad classes, the first being viscose and the second being solvent-process regenerated cellulose fibers. Viscose has long-term production characteristics of high energy consumption, high pollution, complex process and the like, so the yield scale of the viscose has to be controlled, and the viscose has the disadvantages of low wet modulus, dry strength, wet strength and the like. In the production process of the solvent method regenerated cellulose fiber, N-methylmorpholine-N-oxide is used as a solvent, and some functional materials can be added, so that the whole production process has no chemical reaction, no industrial pollution in production, low energy consumption and simple process, and the fiber produced by the solvent method is green and environment-friendly, and has the advantages of high wet modulus, high dry strength and high wet strength and has a functional effect.
Disclosure of Invention
The invention aims to provide a preparation method of a solvent method high wet modulus chitin fiber. The method has the advantages of simple operation, no industrial pollution production, low energy consumption and high safety performance, and is suitable for manufacturing the solvent method high wet modulus chitin fiber in large-scale industrial continuous production.
The preparation method of the solvent method high wet modulus chitin fiber comprises the following steps:
(A) activation of
Adding pulp with the polymerization degree of 300-1500 into process water, adjusting the pH value to 4-6, and adding cellulase for activation; adding alkali to adjust the pH value to 9-13, and stopping activation to obtain slurry porridge;
(B) squeezing machine
Squeezing and dehydrating the slurry porridge to obtain water-containing cellulose with the water content of 10-60 wt% (wt% in the invention represents mass percentage, the same below);
(C) predissolving
Mixing the water-containing cellulose with an N-methylmorpholine-N-oxide aqueous solution with the concentration of 50-88 wt% and a chitin aqueous solution with the concentration of 1-10 wt% to obtain pre-dissolving pulp;
(D) dissolution
Feeding the pre-dissolved slurry into a dissolving machine, heating and vacuumizing, and dehydrating, dissolving, homogenizing and defoaming to obtain slurry;
(E) spinning
And spinning by adopting the slurry to obtain the solvent-process high wet modulus chitin fiber.
With respect to the step (A),
the activation process flow in the invention is simple, the addition of chemical reagents is less, the whole flow is about 1 hour, the time consumption is short, and the operation is convenient. The process is as follows:
preparing process water → adding pulp → adjusting pH value → adding cellulose → terminating activation.
Preferably, the process water parameters are as follows: electrical conductivity of<5μs/cm2The pH value is 6-8, and the temperature is 20-80 ℃. The process water can be deionized water, and the conductivity must be low, which indicates that the metal ions are low. In the invention, the high metal ion in the process water can cause that the polymerization degree can be rapidly and greatly reduced after the pulp is prepared into slurry, so that the slurry quality is uncontrollable and the forming and wire drawing are difficult.
Preferably, the polymerization degree of the pulp is preferably 400 to 800. The polymerization degree of the raw material pulp has direct relation with the index performance of the spinning forming and the fiber finished product. The polymerization degree of the raw material pulp is too low, the pulp is difficult to form and draw wires when the pulp reaches spinning, the strength of the formed fiber is reduced along with the reduction of the polymerization degree, and the low-strength fiber is easy to deform. If the polymerization degree of the raw material pulp is too high, the effect of dissolving the pulp by using the N-methylmorpholine-N-oxide aqueous solution is poor, and the viscosity of the dissolved pulp is very high, so that the flowability is poor, and the spinning forming and spinning states are poor.
Preferably, the pulp can be wood pulp, bamboo pulp and other common pulp.
Preferably, the cellulase is a liquid fiberAnd (3) a protease. Can adopt the product provided by BIOPRACT of supplier with the name of
AL70, product number IPL 5B 06610.
In the activation process of the step (A), the pH value is firstly adjusted to be 4-6 because the cellulase has the best activity under the condition, and the opening of chemical molecular bonds among celluloses in the pulp is facilitated. And after the cellulose activation is finished, adjusting the pH value of the alkali liquor to 9-13 so as to deactivate the cellulase and not to open molecular bonds between the celluloses any more.
With respect to the step (B),
preferably, vacuum dewatering squeezing can be adopted, and dewatering efficiency is improved.
Preferably, after dehydration, the aqueous cellulose is subjected to a comminution treatment prior to dissolution in step (C); the size of the aqueous cellulose particles after comminution is preferably 3cm by 3 cm.
The purpose of controlling the moisture content of the cellulose and the size state of the cellulose in the squeezing stage is to prepare stable and uniform pre-dissolved pulp in the next working section, and stable spinning pulp can be formed only if the pre-dissolved pulp is uniform and stable. If the water content is too high, the steam energy consumption is increased, the size of the water-containing cellulose is too large, the pre-dissolved pulp is not uniform, the quality of the pulp is unstable, and the spinning forming is influenced.
With respect to the step (C),
the invention particularly adds the step of pre-dissolving, which is not only beneficial to stabilizing the quality of the pulp, but also beneficial to dissolving, and the quality of the pulp is improved, so that high-quality fibers can be made.
Preferably, the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is 1: 2-12, preferably 1: 3-5, and more preferably 3.5-4. The N-methylmorpholine-N-oxide aqueous solution with the mass percent of 50-88% is adopted, so that the pulp swelling is facilitated, and the dissolving uniformity and the slurry stability are facilitated. The quality of the slurry is improved, and a high-quality finished product can be made. If the aqueous solution of N-methylmorpholine-N-oxide with the concentration of less than 50 wt% is adopted, the burden of dissolving equipment is large when the next working section is dissolved, the equipment design capacity is exceeded, the slurry cannot be dissolved, and the low concentration causes the increase of the electric quantity and the steam energy consumption during the dissolution. The N-methylmorpholine-N-oxide aqueous solution with the concentration of more than 88 wt% does not achieve the technical strength at home and abroad. Meanwhile, the proportion also needs to be controlled, the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is higher than 1: 2, so that the slurry can not be completely dissolved, and the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is lower than 1: 12, so that the viscosity of the slurry is low, and the spinning and forming can not be carried out.
The chitin added in the step (3) is a functional substance and has antibacterial and bactericidal effects, and the addition of the chitin aqueous solution is beneficial to forming a cellulose mixed phase state and forming and processing fibers.
Preferably, the mass ratio of the water-containing cellulose to the chitin aqueous solution is 1: 0.07-0.2, preferably 1: 0.07-0.16.
Preferably, the cellulose content of the pre-dissolving pulp prepared in the step (C) is 8-12 wt%. The cellulose content is lower than 8 wt%, which causes low slurry viscosity and poor spinning forming state, and the cellulose mass content is higher than 12 wt%, which causes high slurry viscosity and poor spinning forming state.
Preferably, the pH value of the pre-dissolving pulp prepared in the step (C) is 8-12. When the pH value is lower than 8, the N-methylmorpholine-N-oxide aqueous solution is easy to decompose, a byproduct is generated, and the cellulose cannot be normally dissolved.
Preferably, the temperature of the pre-dissolving pulp prepared in the step (C) when the pre-dissolving pulp is sent into the dissolving machine in the step (D) is 50-90 ℃. The temperature of the pre-dissolving pulp is lower than 50 ℃, so that the steam energy consumption is multiplied when the lower working section is dissolved; the temperature of the pre-dissolving pulp is higher than 90 ℃, so that the pulp is dissolved in advance when being dissolved in the next section, the dissolving time is too long, the pulp is dissolved excessively, and the pulp becomes waste which cannot be used for spinning.
All the parameters of the pre-dissolving step are the basis for preparing stable slurry in the next working section. For example, the mass ratio of the aqueous cellulose to the N-methylmorpholine-N-oxide aqueous solution is higher than 1: 2, so that the slurry can not be completely dissolved, and the mass ratio of the aqueous cellulose to the N-methylmorpholine-N-oxide aqueous solution is lower than 1: 12, so that the slurry has low viscosity and can not be spun and formed. The outlet temperature of the pre-dissolving pulp is lower than 50 ℃, the steam energy consumption is multiplied when the lower working section is dissolved, the outlet temperature is higher than 90 ℃, the lower working section is dissolved in advance, the dissolving time is too long, the pulp is excessively dissolved, and the pulp becomes waste which can not be used for spinning. The mass content of the cellulose is lower than 8%, so that the viscosity of the slurry is low, the spinning forming state is poor, the mass content of the cellulose is higher than 12%, the viscosity of the slurry is high, and the spinning forming state is poor. When the pH value is lower than 8, the N-methylmorpholine-N-oxide aqueous solution is easy to decompose, a byproduct is generated, and the cellulose cannot be normally dissolved.
With regard to the step (D),
preferably, the parameters of the dissolver are set to be 1.0-15 kpa of vacuum degree and 60-120 ℃. These parameters are also the basis for making stable slurries. The vacuum degree is lower than 1kpa, and the production can be realized, only in southern areas, the altitude is lower, and the equipment can hardly reach the low vacuum degree. The vacuum degree is higher than 15kpa, so that the solution of the slurry is not completely dissolved, and the spinning cannot be formed. When the temperature is lower than 60 ℃, the time period for dissolving the cellulose into the slurry is increased, so that the productivity is reduced, and the unit time cost is increased. The temperature is higher than 120 ℃, so that the danger in the production process is increased, the slurry is in a static state for a long time, and the explosion is easy to occur at high temperature.
Preferably, the cellulose content of the slurry prepared in the step (D) is 11-15 wt%. This parameter is a key indicator of the use of the dope for spinning formation. The mass content of the cellulose is lower than 11%, so that the viscosity of the slurry is low, the spinning forming state is poor, the mass content of the cellulose is higher than 15%, the viscosity of the slurry is high, and the spinning forming state is poor.
Preferably, the chitin content of the slurry prepared in the step (D) is 0.15-0.25 wt%, preferably 0.19-0.2 wt%. The chitin content of the slurry is directly related to the chitin content in the fiber after spinning, and the amount of the chitin content directly influences the bacteriostatic and bactericidal effects of the fiber.
With respect to the step (E),
preferably, the step (E) is specifically: conveying the slurry by a booster pump, feeding the slurry into a metering pump, spraying the slurry out by a spinneret plate, and performing dry-wet spinning molding to obtain the solvent-process high wet modulus chitin fiber; the spinning speed is 35-100 m/min, the spinning air gap is 5-50 mm, the spinning blowing temperature is 10-30 ℃, the spinning blowing flow is 100-500L/H, the blowing relative humidity is 50-80%, the coagulation bath concentration is 10-30%, and the coagulation bath temperature is 5-30 ℃. The parameters are technical package parameters of the spinning forming of the section, and the parameters are combined with each other, and any technical parameter is lacked, so that the good spinning forming of the slurry cannot be realized, and the physical index of the fiber is good.
Furthermore, the slurry can be sent to a filter to remove impurities in the pulp raw material before being sent to the booster pump.
The activation of the step (A) to the spinning of the step (E) is the key step of the invention, and the innovation points of the method of the invention are as follows: the product produced by the steps has safer production process route and stable quality index of the produced product. The above steps are all indispensable, for example, when the activation process of the step (A) is absent, the solution can not be dissolved into slurry which can be used for spinning formation when the step (D) is dissolved, the solvent-process chitin fiber with high wet modulus can not be produced, and the colloquially speaking is that the dissolved slurry is unqualified, which belongs to waste materials. The reason is that the pulp is activated in the step (A), chemical molecular bonds between cellulose molecules and molecules are opened, so that when the pulp is pre-dissolved in the step (C), 50-88 wt% of N-methylmorpholine-N-oxide aqueous solution can uniformly enter the fiber molecules, and the pulp for spinning can be prepared by matching with the dissolving process in the step (D). According to experimental results, the solvent-process high wet modulus chitin fiber is finally spun through repeated parameter adjustment and groping optimization after a plurality of tests are carried out on a production line.
In some preferred embodiments of the present invention, the method further comprises the steps of:
(F) washing with water
And conveying the solvent-process high wet modulus chitin fiber formed by spinning into a water bath at the temperature of 20-80 ℃ for washing.
Preferably, deionized water is used for washing. After the fiber is washed by water, the solvent N-methylmorpholine-N-oxide can be recovered, and the recovery rate of the solvent is improved.
In some preferred embodiments of the present invention, the method further comprises the steps of:
(G) oiling
And (3) oiling the washed high wet modulus chitin fiber by a solvent method, wherein the circulating concentration of the oiling agent is 0.5-5 wt%, the circulating pH value of the oiling agent is 6-9, and the circulating temperature of the oiling agent is 20-80 ℃.
Preferably, the oil agent is selected from one or two or more of LeminOR, LeminWG and LeminAN produced by CLARIANT manufacturer. The three kinds of oil agents can be deteriorated when the pH value is not in the range of 6-9, so that the effective components are reduced. The temperature is not higher than 80 ℃, and the deterioration and the reduction of effective components can be generated when the temperature is higher than 80 ℃. The mass concentration of the oil agent is added according to the requirement of a client on the oil content of the fiber.
In some preferred embodiments of the present invention, the method further comprises the steps of:
(H) drying by baking
Preferably, the drying temperature is 80-150 ℃.
And heating the oiled fiber to reach the required fiber water content. In some preferred embodiments of the invention, 4 ovens are used in series, and each oven is independently controlled in temperature, wherein the drying temperature is used for ensuring that the moisture content of the product meets the requirement.
The invention also aims to provide the solvent-process high wet modulus chitin fiber prepared by any one of the methods, which has higher wet modulus, contains chitin, has certain antibacterial and bactericidal effects, and has good moisture absorption, sweat releasing, air permeability, wearing comfort, soft hand feeling, contribution to continuous dyeing, contribution to printing and dyeing and contribution to producing high-end fabrics.
The advantages of the invention are mainly embodied in the following aspects:
1. the preparation method has the advantages of simple operation, no industrial pollution, low energy consumption and high safety performance, and is suitable for manufacturing the solvent method high wet modulus chitin fiber in large-scale industrial continuous production;
2. the preparation method of the invention can not destroy the natural characteristics of the fiber, and the chitin fiber prepared by the method can effectively keep the original elasticity, hygroscopicity and softness, has no harmful chemical residues, and also has certain antibacterial and bacteriostatic effects;
3. the solvent method high wet modulus chitin fiber prepared by the invention has higher wet modulus which is more than or equal to 15cn/dtex, and the product prepared by the solvent method high wet modulus chitin fiber prepared by the invention has certain antibacterial and bactericidal effects, good moisture absorption and sweat releasing properties, good air permeability, comfortable wearing, soft hand feeling, and is beneficial to continuous dyeing, printing and dyeing and production of high-end fabrics.
Detailed Description
The present invention is further described with reference to the following embodiments, but the present invention is not limited to the following embodiments, and any technical solutions implemented by modifications, substitutions or alterations based on the technical basic idea of the present invention are within the scope of the present invention.
A preparation method of solvent method high wet modulus chitin fiber comprises the following steps:
(A) activation of
The activation process has the advantages of simple flow, less chemical reagent addition, short time consumption and convenient operation, and the whole flow is about 1 hour. The process is as follows:
preparing process water → adding pulp → adjusting pH value → adding cellulose → terminating activation.
Wherein, the blending process water: deionized water is adopted as process water; the parameter requirements are as follows: electrical conductivity of<5μs/cm2The pH value is 6-8, and the temperature is 20-80 ℃.
Adding pulp: the polymerization degree of the wood pulp or the bamboo pulp is 300-1500.
Adjusting the pH value: and adjusting the pH value to 4-6 by using acid and alkali.
Adding cellulase: adopts liquid cellulase, and can select commercial trade name
AL70, product number IPL 5B06610, supplier bioprac.
And (3) stopping activation: adding alkali to adjust the pH value to 9-13.
(B) Squeezing machine
After the pulp congee is dehydrated and squeezed in vacuum, the moisture content required by the process is obtained, and then the pulp congee is crushed to obtain the water-containing cellulose;
parameters are as follows: the water content of the water-containing cellulose is 10-60 wt%, and the size of the water-containing cellulose after being crushed is 3cm x 3 cm.
(C) Predissolving
The addition of a pre-dissolution step in the present invention is particularly advantageous not only for stabilizing the slurry quality but also for dissolution. The quality of the slurry is improved, and high-quality fibers can be made. The method comprises the following steps: mixing the water-containing cellulose with an N-methylmorpholine-N-oxide aqueous solution with the concentration of 50-88 wt% and a chitin aqueous solution with the concentration of 1-10 wt% to obtain pre-dissolving pulp; the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is 1: 2-12, and the mass ratio of the water-containing cellulose to the chitin aqueous solution is 1: 0.07-0.15.
Parameters are as follows: the outlet temperature of the pre-dissolving pulp is 50-90 ℃, the cellulose content is 8-12 wt%, and the pH is 8-12.
(D) Dissolution
The pre-dissolved slurry enters a dissolving machine, and is heated, vacuumized, dehydrated, dissolved, homogenized and defoamed to obtain amber transparent and homogeneous slurry. Parameters are as follows: the vacuum degree is 1.0-15.0 kpa, the temperature is 60-120 ℃, and the slurry composition is as follows: the cellulose content is 11-15 wt%.
(E) Spinning
Conveying the pulp to a filter, filtering to remove impurities in the pulp raw material, conveying the pulp raw material by a booster pump, feeding the pulp raw material into a metering pump, spraying the pulp raw material by a spinneret plate, and performing dry-wet spinning forming; parameters are as follows: the spinning speed is 35-100 m/min, the spinning air gap is 5-50 mm, the spinning blowing temperature is 10-30 ℃, the spinning blowing flow is 100-500L/H, the blowing relative humidity is 50-80%, the coagulation bath concentration is 10-30%, and the coagulation bath temperature is 5-30 ℃.
(F) Washing with water
After the fiber is washed by water, the solvent N-methylmorpholine-N-oxide is recovered, and the recovery rate of the solvent is improved; parameters are as follows: the washing temperature is 20-80 ℃.
(G) Oiling
After oiling, the fiber reaches the required oiling rate; parameters are as follows: the circulating concentration of the oil agent is 0.5-5%, the circulating pH value of the oil agent is 6-9, and the circulating temperature of the oil agent is 20-80 ℃; the oil agent is selected from manufacturers: LeminoR, LeminWG and LeminAN produced by Clariant.
(H) Drying by baking
Heating the oiled fiber to reach the required fiber water content; parameters are as follows: the drying temperature is 80-150 ℃.
Example 1
Adding pulp with polymerization degree of 500 to the conductivity<5μs/cm2The pH value is as follows: 6.8, temperature: adjusting the pH value to 5 in process water at 50 ℃, adding cellulase for activation for one hour, adding sodium hydroxide for stopping activation, and adjusting the pH value to 10.5; after the activated pulp congee is subjected to vacuum dehydration and squeezing, controlling the water content of the water-containing cellulose to be 48 wt%, and crushing the cellulose into 3 cm-3 cm particles; then adding 5 wt% chitin aqueous solution and 81 wt% N-methylmorpholine-N-oxide aqueous solution, wherein the mass ratio of the water-containing cellulose to the chitin aqueous solution is 1: 0.16, the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is 1: 3.7, and obtaining pre-dissolving pulp after pulp swelling; the outlet temperature of the pre-dissolving pulp is 70 ℃, and the composition of the pre-dissolving pulp is as follows: cellulose 10.2 wt%, pH 9.5. Feeding the pre-dissolved pulp into a dissolving machine, and controlling the vacuum degree to be 4.0 kpa; slurry composition obtained by dissolution: 12.7 percent of cellulose and 0.195 percent of chitin.
Conveying the pulp to a filter, filtering to remove impurities in the pulp raw material, conveying the pulp raw material by a booster pump, spraying the pulp raw material by a spinneret plate, and performing dry-wet spinning forming, wherein the spinning speed is 50m/min, the spinning air gap is 10mm, the spinning blowing temperature is 14 ℃, the spinning blowing flow is 250L/H, the blowing relative humidity is 50%, the coagulation bath concentration is 15%, the coagulation bath temperature is 10 ℃, and the fiber is washed by water at the washing temperature of 60 ℃; oiling the washed fiber, wherein the circulating concentration of the oiling agent is 1.0 percent, the circulating pH value of the oiling agent is 6.5, and the circulating temperature of the oiling agent is 50 ℃; drying the oiled fiber at 100 ℃ to obtain the finished fiber.
The fiber test results are as follows:
the titer is 1.56dtex, the dry breaking strength is 3.6cN/dtex, the wet breaking strength is 3.0cN/dtex, the dry elongation at break is 16.8%, the wet elongation at break is 19.2%, the wet modulus is 16.6cN/dtex, the dry strength variation coefficient is 10%, the whiteness is 68%, the oil content is 0.23%, and the moisture regain is 11.2%;
the bacteriostasis value is more than or equal to 2.0, the sterilization value is more than 0 (the bacteriostasis detects staphylococcus aureus ATCC 6538, the bacteriostasis value is more than or equal to 2.0, which indicates that the bacteriostasis effect is tested, the sterilization value is more than 0, which indicates that the sterilization effect is tested, and the same follows).
Example 2
Adding pulp with polymerization degree 550 into the mixture to obtain the mixture with electric conductivity<5μs/cm2The pH value is as follows: 6.0, temperature: adjusting pH value to 4.5 in process water at 50 ℃, adding cellulase for activation for one hour, adding sodium hydroxide to stop activation, and adjusting pH value to 11; after the activated pulp congee is subjected to vacuum dehydration and squeezing, controlling the water content of the water-containing cellulose to be 53 wt%, and crushing the cellulose into 3 cm-3 cm particles; then adding 7 wt% of chitin aqueous solution and 85 wt% of N-methylmorpholine-N-oxide aqueous solution, wherein the mass ratio of the water-containing cellulose to the chitin aqueous solution is 1: 0.1, the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is 1: 3.2, and obtaining pre-dissolving pulp after pulp swelling; the outlet temperature of the pre-dissolving pulp is 68 ℃, and the composition of the pre-dissolving pulp is as follows: cellulose 10.45%, pH 9.0. Feeding the pre-dissolved pulp into a dissolving machine, and controlling the vacuum degree to be 4.5 kpa; slurry composition obtained by dissolution: 12.7 percent of cellulose and 0.195 percent of chitin.
Conveying the pulp to a filter, filtering to remove impurities in the pulp raw material, conveying the pulp raw material by a booster pump, spraying the pulp raw material by a spinneret plate, and performing dry-wet spinning forming, wherein the spinning speed is 40m/min, the spinning air gap is 20mm, the spinning blowing temperature is 16 ℃, the spinning blowing flow is 350L/H, the blowing relative humidity is 60%, the coagulation bath concentration is 15%, the coagulation bath temperature is 10 ℃, and the fiber is washed by water at the washing temperature of 40 ℃; oiling the washed fiber, wherein the circulating concentration of the oiling agent is 1.8 percent, the circulating pH value of the oiling agent is 7.0, and the circulating temperature of the oiling agent is 50 ℃; drying the oiled fiber at 110 ℃ to obtain the finished fiber.
The fiber test results are as follows:
the titer is 2.3dtex, the dry breaking strength is 3.3cN/dtex, the wet breaking strength is 2.8cN/dtex, the dry elongation at break is 17.2%, the wet elongation at break is 19.4%, the wet modulus is 14.3cN/dtex, the dry strength variation coefficient is 12%, the whiteness is 65%, the oil content is 0.25%, and the moisture regain is 10.5%.
The bacteriostatic value is more than or equal to 2.0, and the sterilization value is more than 0.
Example 3
Adding pulp with polymerization degree of 600 to the conductivity<5μs/cm2The pH value is as follows: 7.3, temperature: adjusting the pH value to 5.2 in process water at 50 ℃, adding cellulase for activation for one hour, adding sodium hydroxide for stopping activation, and adjusting the pH value to 11.5; after the activated pulp congee is subjected to vacuum dehydration and squeezing, controlling the water content of the water-containing cellulose to be 50 wt%, and crushing the cellulose into 3 cm-3 cm particles; then adding 10 wt% chitin aqueous solution and 60 wt% N-methylmorpholine-N-oxide aqueous solution, wherein the mass ratio of the water-containing cellulose to the chitin aqueous solution is 1: 0.07, the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is 1: 4.8, and obtaining pre-dissolving pulp after pulp swelling; the outlet temperature of the pre-dissolving pulp is 68 ℃, and the composition of the pre-dissolving pulp is as follows: cellulose 8.2%, pH 10. Feeding the pre-dissolved pulp into a dissolving machine, and controlling the vacuum degree to be 4.0 kpa; slurry composition obtained by dissolution: 12.7 percent of cellulose and 0.195 percent of chitin.
Conveying the pulp to a filter, filtering to remove impurities in the pulp raw material, conveying the pulp raw material by a booster pump, spraying the pulp raw material by a spinneret plate, and performing dry-wet spinning forming, wherein the spinning speed is 35m/min, the spinning air gap is 35mm, the spinning blowing temperature is 18 ℃, the spinning blowing flow is 500L/H, the blowing relative humidity is 68%, the coagulation bath concentration is 23%, the coagulation bath temperature is 13 ℃, and the fiber is washed by water at 50 ℃; oiling the washed fiber, wherein the circulating concentration of the oiling agent is 3.0 percent, the circulating pH value of the oiling agent is 7.9, and the circulating temperature of the oiling agent is 55 ℃; drying the oiled fiber at 105 ℃ to obtain the finished fiber.
The fiber test results are as follows:
the titer is 3.8dtex, the dry breaking strength is 3.08cN/dtex, the wet breaking strength is 2.65cN/dtex, the dry elongation at break is 16.4%, the wet elongation at break is 18.8%, the wet modulus is 15.9cN/dtex, the dry strength variation coefficient is 15%, the whiteness is 60%, the oil content is 0.3%, and the moisture regain is 11%.
The bacteriostatic value is more than or equal to 2.0, and the sterilization value is more than 0.
Comparative example 1
Adding pulp with polymerization degree of 500 to the conductivity<5μs/cm2The pH value is as follows: 6.8, temperature: adjusting the pH value to 5 in process water at 50 ℃, adding cellulase for activation for one hour, adding sodium hydroxide for stopping activation, and adjusting the pH value to 10.5; after the activated pulp congee is subjected to vacuum dehydration and squeezing, controlling the water content of the water-containing cellulose to be 48 wt%, and crushing the cellulose into 3 cm-3 cm particles; then adding 81 wt% of N-methylmorpholine-N-oxide aqueous solution, wherein the mass ratio of the water cellulose to the N-methylmorpholine-N-oxide aqueous solution is 1: 3.7, and obtaining pre-dissolved pulp after pulp swelling; the outlet temperature of the pre-dissolving pulp is 70 ℃, and the composition of the pre-dissolving pulp is as follows: cellulose 10.9 wt%, pH 9.5. Feeding the pre-dissolved pulp into a dissolving machine, and controlling the vacuum degree to be 4.0 kpa; slurry composition obtained by dissolution: 13.0 percent of cellulose.
Conveying the pulp to a filter, filtering to remove impurities in the pulp raw material, conveying the pulp raw material by a booster pump, spraying the pulp raw material by a spinneret plate, and performing dry-wet spinning forming, wherein the spinning speed is 50m/min, the spinning air gap is 10mm, the spinning blowing temperature is 14 ℃, the spinning blowing flow is 250L/H, the blowing relative humidity is 50%, the coagulation bath concentration is 15%, the coagulation bath temperature is 10 ℃, and the fiber is washed by water at the washing temperature of 60 ℃; oiling the washed fiber, wherein the circulating concentration of the oiling agent is 1.0 percent, the circulating pH value of the oiling agent is 6.5, and the circulating temperature of the oiling agent is 50 ℃; drying the oiled fiber at 100 ℃ to obtain the finished fiber.
The test results are as follows:
the titer is 1.65dtex, the dry breaking strength is 3.68cN/dtex, the wet breaking strength is 3.08cN/dtex, the dry elongation at break is 16.8%, the wet elongation at break is 19.2%, the wet modulus is 16.6cN/dtex, the dry strength variation coefficient is 10%, the whiteness is 68%, the oil content is 0.23%, and the moisture regain is 11.2%.
Because chitin is not added, the antibacterial property of the fiber is not shown.
Comparative example 2
Adding pulp with polymerization degree of 500 to the conductivity<5μs/cm2The pH value is as follows: 6.8, temperature: adjusting the pH value to 5 in process water at 50 ℃, adding cellulase for activation for one hour, adding sodium hydroxide for stopping activation, and adjusting the pH value to 10.5; after the activated pulp congee is subjected to vacuum dehydration and squeezing, controlling the water content of the water-containing cellulose to be 48 wt%, and crushing the cellulose into 3 cm-3 cm particles; then adding 5 wt% chitin aqueous solution and 81 wt% N-methylmorpholine-N-oxide aqueous solution, wherein the mass ratio of the water-containing cellulose to the chitin aqueous solution is 1: 0.08, the mass ratio of the water-containing cellulose to the N-methylmorpholine-N-oxide aqueous solution is 1: 3.7, and obtaining pre-dissolving pulp after pulp swelling; the outlet temperature of the pre-dissolving pulp is 70 ℃, and the composition of the pre-dissolving pulp is as follows: cellulose 10.4 wt%, pH 9.5. Feeding the pre-dissolved pulp into a dissolving machine, and controlling the vacuum degree to be 4.0 kpa; slurry composition obtained by dissolution: 12.9 percent of cellulose and 0.10 percent of chitin.
Conveying the pulp to a filter, filtering to remove impurities in the pulp raw material, conveying the pulp raw material by a booster pump, spraying the pulp raw material by a spinneret plate, and performing dry-wet spinning forming, wherein the spinning speed is 50m/min, the spinning air gap is 10mm, the spinning blowing temperature is 14 ℃, the spinning blowing flow is 250L/H, the blowing relative humidity is 50%, the coagulation bath concentration is 15%, the coagulation bath temperature is 10 ℃, and the fiber is washed by water at the washing temperature of 60 ℃; oiling the washed fiber, wherein the circulating concentration of the oiling agent is 1.0 percent, the circulating pH value of the oiling agent is 6.5, and the circulating temperature of the oiling agent is 50 ℃; drying the oiled fiber at 125 ℃ to obtain the finished fiber.
The functional test results are as follows:
the titer is 1.56dtex, the dry breaking strength is 3.6cN/dtex, the wet breaking strength is 3.0cN/dtex, the dry elongation at break is 16.8%, the wet elongation at break is 19.2%, the wet modulus is 16.6cN/dtex, the dry strength variation coefficient is 10%, the whiteness is 68%, the oil content is 0.23%, and the moisture regain is 11.2%.
The bacteriostatic value is more than or equal to 1.0, and the bactericidal value is 0. Because the addition amount of chitin is reduced, the functionality of chitin does not reach the antibacterial effect.
The results of the functional tests on the solvent-process high wet modulus chitin fibers produced in examples 1-3 and the fibers of comparative examples 1-2 are summarized and compared in Table 1 below.
TABLE 1 functional test results for fiber products of examples 1-3 and comparative examples 1-2
The data show that the chitin component in the solvent-process high wet modulus chitin fiber prepared by the invention can be stabilized at the addition of 0.195 percent and has higher wet modulus which is more than or equal to 14 cN/dtex. The dry breaking strength and the wet breaking strength of the fiber are high. The fiber has obvious antibacterial property, the antibacterial value is more than or equal to 2.0, and the antibacterial value is more than 0.
Claims (10)
1. A preparation method of solvent method high wet modulus chitin fiber is characterized by comprising the following steps:
(A) activation of
Adding pulp with the polymerization degree of 300-1500 into process water, adjusting the pH value to 4-6, and adding cellulase for activation; adding alkali to adjust the pH value to 9-13, and stopping activation to obtain slurry porridge;
(B) squeezing machine
Squeezing and dehydrating the slurry porridge to obtain water-containing cellulose with the water content of 10-60 wt%;
(C) predissolving
Mixing the water-containing cellulose with an N-methylmorpholine-N-oxide aqueous solution with the concentration of 50-88 wt% and a chitin aqueous solution with the concentration of 1-10 wt% to obtain pre-dissolving pulp;
(D) dissolution
Feeding the pre-dissolved slurry into a dissolving machine, heating and vacuumizing, and dehydrating, dissolving, homogenizing and defoaming to obtain slurry;
(E) spinning
And spinning by adopting the slurry to obtain the solvent-process high wet modulus chitin fiber.
2. The method of claim 1, wherein in step (a), the process water parameters are: electrical conductivity of<5μs/cm2The pH value is 6-8, and the temperature is 20-80 ℃.
3. The method according to claim 1, wherein in the step (C), the mass ratio of the aqueous cellulose to the aqueous solution of N-methylmorpholine-N-oxide is 1: 2 to 12; the mass ratio of the water-containing cellulose to the chitin aqueous solution is 1: 0.07-0.15.
4. The method of claim 1, wherein the pre-dissolved pulp produced in step (C) has a cellulose content of 8 to 12 wt% and a pH of 8 to 12.
5. The method of claim 1, wherein the pre-dissolving pulp produced in step (C) is fed to the dissolver in step (D) at a temperature of 50 to 90 ℃; in the step (D), parameters of a dissolving machine are set as follows: the vacuum degree is 1.0-15 kpa, and the temperature is 60-120 ℃.
6. The method of claim 1, wherein the slurry produced in step (D) has a cellulose content of 11 to 15 wt% and a chitin content of 0.15 to 0.25 wt%.
7. The method of claim 1, wherein step (E) is specifically: conveying the slurry by a booster pump, feeding the slurry into a metering pump, spraying the slurry out by a spinneret plate, and performing dry-wet spinning molding to obtain the solvent-process high wet modulus chitin fiber; the spinning parameters are as follows: the spinning speed is 35-100 m/min, the spinning air gap is 5-50 mm, the spinning blowing temperature is 10-30 ℃, the spinning blowing flow is 100-500L/H, the blowing relative humidity is 50-80%, the coagulation bath concentration is 10-30%, and the coagulation bath temperature is 5-30 ℃.
8. The method of claim 1, further comprising the step of:
(F) washing with water
And conveying the solvent-process high wet modulus chitin fiber formed by spinning into a water bath at the temperature of 20-80 ℃ for washing.
9. The method of claim 8, further comprising the step of:
(G) oiling
Oiling treatment is carried out on the washed chitin fibers with high wet modulus by a solvent method, the circulating concentration of an oiling agent is 0.5-5%, the circulating pH value of the oiling agent is 6-9, and the circulating temperature of the oiling agent is 20-80 ℃;
(H) drying by baking
The drying temperature is 80-150 ℃.
10. A solvent-process high wet modulus chitin fiber, which is characterized by being prepared by the method of any one of claims 1-9.
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