CN110952159A

CN110952159A - Application of silk fibroin solution in preparation of regenerated cellulose fiber

Info

Publication number: CN110952159A
Application number: CN201910943380.5A
Authority: CN
Inventors: 黄效华; 刘彦明; 甄丽; 刘洁; 王瑞玲
Original assignee: Qingdao Baicao New Material Co ltd
Current assignee: Bestee Material Tsingtao Co Ltd
Priority date: 2017-07-06
Filing date: 2017-07-06
Publication date: 2020-04-03
Anticipated expiration: 2037-07-06
Also published as: CN110952158A; CN107142542B; CN107142542A; CN110952159B; CN110952158B

Abstract

The invention provides an application of a silk fibroin solution in preparation of regenerated cellulose fiber, which comprises the following steps: (1) the hemp pulp is adopted to be prepared into hemp pulp after pre-crushing, cellulose activation, primary pressing, alkali liquor impregnation, secondary pressing, crushing, ageing and alkali liquor dissolution; (2) the prepared jute pulp is made into jute pulp cellulose sulfonate solution through the reaction with carbon disulfide; (3) adding a silk fibroin solution into a hemp pulp cellulose sulfonate solution to prepare a spinning solution; (4) filtering, defoaming, spinning and post-treating the spinning solution to prepare fibroin regenerated cellulose fiber; in the process of the invention, the preparation of the silk fibroin solution reserves the colloid on the surface of the silk, and the colloid on the surface of the silk can be combined with fiber molecules in the fiber amorphous region during fiber forming, thereby further improving the strength of the fiber.

Description

Application of silk fibroin solution in preparation of regenerated cellulose fiber

Parent patent name: a fibroin regenerated cellulose fiber and a preparation method thereof; parent patent application No.: 201710544939.8, respectively; patent application date of the parent: 7 and 6 months in 2017.

Technical Field

The invention relates to a cellulose fiber and a preparation method thereof, in particular to an application of a silk fibroin solution in the preparation of regenerated cellulose fiber.

Background

Protein fibers, fibers made from natural proteins that behave like wool. Wool, silk and the like are natural protein fibers. The first successful in 1866 british e.e. hous produced man-made protein fibers from animal glue. The animal glue is dissolved in acetic acid, coagulated and drawn in an aqueous solution of nitrate, and then denitrified by a ferrous salt solution, and further processed to obtain the protein fiber, but the protein fiber is not industrialized. Frattis in 1935 italy made artificial wool from casein extracted from cow milk. Protein fibers made of natural proteins have properties comparable to wool. The basic structural units are all high molecules which are amino acids and are bonded together by amide bonds (peptide bonds). Compared with natural wool, the wool has the advantages of difficult shrinkage, difficult worm damage and easy storage; the disadvantage is that the warmth retention property and softness are inferior to those of natural wool. The main raw materials for industrial production of protein fiber are casein, peanut protein, soybean protein, etc.

Protein fibers represented by polylactic acid and silk contain a large amount of amino acids, have good compatibility with human bodies, and have a natural nourishing effect on human bodies, so the protein fibers are often used for manufacturing masks, underwear, medical supplies and the like, but the polylactic acid fibers are high in price in China, the process production is not popularized in China, and real silk such as silk is high in price and is not suitable for mass production.

The patent application No. 200710097723.8, entitled "method for producing protein viscose fiber from animal protein and plant fiber", uses animal hair, skin, etc. as raw material, extracts animal protein and alpha cellulose, and co-spins them in acid bath, the ratio of protein liquid and alpha cellulose is 3: 7-3.5: 6.5. The denatured protein liquid is mixed in a mixing section in the flow of a five-in-one machine method to form protein viscose spinning liquid, and then the spinning is carried out after defoaming and ripening.

The manufacturing process of the patent is not environment-friendly, and a large amount of toxic and heavy metal substances are adopted, for example, flammable and explosive volatile acrylonitrile is used in the process of manufacturing the protein liquid. Chromium salts are used for post-treatment protein curing. The substance still remains on the fiber after subsequent water washing, which cannot be realized under the environmental protection pressure of the current practical production, and the heavy metal and toxic substances in the finished product exceed the standard.

Meanwhile, as various animal fur proteins are adopted, the sources are complex, the property and the stability of the protein liquid are very low, the application number is CN201210033741.0, and the invention is named as a production process of the wool protein composite viscose fiber, the wool protein composite viscose fiber is prepared by preparing the wool protein spinning solution and then adding an auxiliary agent, but the phenomena that the scale components on the surface of wool protein are complex, the protein is not uniformly dispersed, a spinning nozzle is easily blocked in the spinning process and the like are still encountered in the production process of the cellulose fiber, and meanwhile, compared with real silk, the prepared wool protein composite viscose fiber has insufficient glossiness, smooth hand feeling, uniform dyeing liquid and large difference compared with real silk.

The application number is 201210387021.4, the name is 'preparation method of fibroin blended regenerated cellulose fiber' and the application number is 201110400581.4, the patent name is 'regenerated animal micro powder protein cellulose fiber and preparation method thereof', the prepared protein cellulose fiber and the like are not high enough in wet breaking strength, and are not the best choice for preparing mask materials.

Disclosure of Invention

In view of the defects of the prior art, the first invention of the invention provides the application of the auxiliary agent liquid in the preparation method of the regenerated cellulose fiber, so that the fabric made of the fiber has good dyeing performance, does not generate the phenomenon of flower color after being dyed and washed, and has good dyeing grade and color change grade.

In order to solve the technical problems, the invention adopts the technical scheme that:

an application of a silk fibroin solution in preparation of regenerated cellulose fiber comprises the following steps:

(1) the hemp pulp is adopted to be prepared into hemp pulp after pre-crushing, cellulose activation, primary pressing, alkali liquor impregnation, secondary pressing, crushing, ageing and alkali liquor dissolution;

(2) the prepared jute pulp is made into jute pulp cellulose sulfonate solution through the reaction with carbon disulfide;

(3) adding a silk fibroin solution into a hemp pulp cellulose sulfonate solution to prepare a spinning solution;

(4) and filtering, defoaming, spinning and post-treating the spinning solution to obtain the fibroin regenerated cellulose fiber.

The hemp pulp has the characteristics of antibiosis and softness of natural hemp fibers, and also has certain natural glossiness, and the cellulose fibers made of the hemp fibers also have the characteristics of softness and good drapability; meanwhile, capillary tubes among jute fiber pulp fibers are smaller than those of the conventional pulp, the structure is compact, the pulp is impregnated by a common impregnation method, the alkali liquor permeation difficulty is higher, the impregnation unevenness is easily caused, the impregnation unevenness directly causes the unevenness of the polymerization degree of the slurry in the subsequent process, the prepared fiber crystallinity difference is larger, a spinning nozzle is easily blocked and is difficult to filter in the spinning process, the subsequent fabric is difficult to dye, the color is easy to generate, and the color fading phenomenon after dyeing is serious; more importantly, the fiber fabric made of the fiber of the invention has uniform and consistent dyeing, no generation of flower materials and no fading during dyeing.

The fibroin regenerated cellulose fiber prepared by the invention meets the following indexes: the dry breaking strength is more than or equal to 3.2cN/dtex, the wet breaking strength is more than or equal to 1.9cN/dtex, the fibroin content is more than or equal to 5 percent, the dry breaking elongation is 12-14 percent, the wet breaking elongation is 17-19 percent, the crystallinity is 40-43 percent, the radial water swelling degree is 25-30 percent, the fineness deviation rate is less than or equal to 1.5 percent, and the residual sulfur content is less than or equal to 5mg/100 g; the fabric made of the fiber is detected by GB/T5713-1997, the color change grade is 4-5 grade, and the staining grade is 4 grade; the color change grade is 5 grade and the staining grade is 3-4 grade by adopting AATCC107-2007 standard for detection; the color change grade of the product is 5 grades, and the staining grade of the product is 4-5 grades by adopting JISL0846-2004 standard detection.

The fibroin regenerated cellulose fiber prepared by the invention contains fibroin more than 5%, the fibroin content is related to the functionality of the cellulose fiber, when the fibroin content is lower than 5%, the functionality of the fibroin is influenced, the prepared fiber has poor antibacterial and other functionalities, and when the fibroin content in the cellulose fiber is higher than 5%, the fiber contains a large amount of amino acid, so that the fibroin regenerated cellulose fiber can supplement protein lacking in skin, and meanwhile, the moisturizing effect is enhanced, and the fibroin regenerated cellulose fiber is preferable for preparing facial masks and underwear; meanwhile, when the fibroin content in the cellulose fiber is more than 5%, the fibroin surface is combined with the cellulose in the amorphous area of the cellulose, so that the breaking strength of the cellulose fiber can be improved, generally the wet breaking strength of the cellulose fiber is not high, but the wet breaking strength of the fibroin regenerated cellulose fiber is more than or equal to 1.9cN/dtex, and the prepared mask is not easy to tear and can form good attachment on the face; the manufactured underwear has good comfort and wrapping property.

Further, the fibroin regenerated cellulose fiber also meets the following indexes:

defects are less than or equal to 1.1mg/100g, long fiber rate is less than or equal to 0.2%, double length fiber is less than or equal to 0.5mg/100mg, length deviation rate is less than or equal to +/-2%, and whiteness is more than or equal to 80%;

in the step (1), the hemp pulp raw material isThe related indexes are that the polymerization degree is 500-600, the ash content is less than 0.8 percent, the α -cellulose content is 93-96 percent, the alkali absorption value is 550-600 percent, the swelling degree (volume) is 300-350 percent, the water content is 8.5 +/-1.0 percent, and the dust is less than or equal to 150mm²Per kg, no more than 0.5 of dust, no more than 20mg/kg of iron, no more than 0.05 percent of ash, no more than 150s of reactivity, no more than 0.2 percent of fatty wax, and a definite volume weight of 600g/m³。

The hemp pulp has the characteristics of antibiosis and softness of natural hemp fibers and certain natural glossiness, the cellulose fibers made of the hemp natural fibers also have the characteristics of softness and good drapability, the hemp pulp is made into the fibers and the natural fibroin to be fused in a microscopic layer to be made into the protein composite fibers with real silk feeling, and the advantages of the hemp cellulose fibers and the silkworm silk are exerted to the maximum extent, so that the fibers prepared by the method have very large market space.

The whole polymerization degree of the hemp pulp is lower than that of the common cotton pulp, the hemp pulp contains colloid, ash and the like which are not contained in the common cotton pulp, and the content of α -cellulose is lower than that of cotton linter and wood pulp, so that the optimal technical parameter proportion is selected, and the preparation of qualified fibroin fibers is particularly important.

The hemp pulp is one or more of jute, ramie, flax, kenaf and hemp; wherein the most preferred cellulose fiber raw materials are jute and kenaf; after the jute and the ambary are made into pulp, the glossiness is higher, the antibacterial property and other functionalities are stronger, and the process is easier to control in the preparation process of the cellulose fiber;

the hemp pulp can endow the fiber with better antibacterial property, glossiness and moisture absorption and air permeability;

in the step (1), a pre-crushing step, namely crushing the hemp pulp into slurry by adopting a crusher, wherein the crushing degree is 350-400 g/L; the slurry with proper concentration is crushed, the reaction surface area is increased, the production efficiency is improved, and necessary conditions are provided for subsequent processes;

in the step (1), the cellulose activation step: adding hydrogen peroxide into the crushed slurry; the concentration of the hydrogen peroxide in the slurry is 15-20 g/L; heating the slurry to 40-55 deg.C in the slurry pool, and stirring for 30-40 min; the hydrogen peroxide has slow and moderate oxidation performance, on one hand, hemicellulose, ash, tannin and colloid in a small part of the hemp pulp fiber are removed, on the other hand, the hydrogen peroxide slowly releases bubbles to attach to the surface of the hemp fiber, the capillary space between the fibers is increased, so that the fibers are filled with micro bubbles, the impregnation uniformity and the reaction performance of the hemp pulp are improved, and the color fastness to washing of the fiber product is further improved; after being activated by cellulose, the degree of polymerization of jute pulp is 450-550.

In the step (1), in the step of primary squeezing, the primary squeezing temperature is 25-30 ℃, and the squeezing multiple is 2-2.3 times; can extrude moisture and hydrogen peroxide in the cellulose activation step, hydrogen peroxide content is lower, therefore the liquid of extruding can recycle, simultaneously behind the cellulose activation step, hydrogen peroxide has increased the interval between the fibrilia, after squeezing, forms "vacuum" state between the fibre, in follow-up impregnation step, alkali lye is very easy to permeate and impregnate, further improves the degree of consistency of impregnating.

The step (1), an alkali liquor dipping step, dipping the hemp pulp in 140g/l NaOH dipping solution with the concentration of 100-;

preferably, an auxiliary agent liquid is added in the impregnation step, and the addition amount of the auxiliary agent liquid is 2-4% of the impregnation alkali liquor; the reaction performance of the pulp is further improved, and the degradation of the hemp pulp in the subsequent steps is reduced; compared with cotton pulp and wood pulp, the polymerization degree of the hemp pulp is easier to degrade after reaching certain conditions; if the cellulose activation is carried out in the early stage without control, the hemp pulp is degraded too violently in the subsequent steps, and finally the fiber strength is lower;

the auxiliary agent liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;

the OS-406 is a high molecular weight polyether surfactant solution sold by Guangzhou New Material science and technology Co., Ltd, and has a pH value of 7-9, an HLB value of 17-18, a viscosity of 600-800 mPa.S (25 ℃), and a surface tension of 20-23 mN/m;

the auxiliary agent liquid comprises the following components in parts by weight: 2-5 parts of OS-406, 0.8-1.5 parts of dibutyl hydroxy toluene, 3-6 parts of ethanol, 1-3 parts of sodium carbonate and 40-50 parts of deionized water.

The addition of the auxiliary agent liquid further improves the reaction performance of the pulp, and the reaction performance can be improved by 5 to 10 percent; meanwhile, the oxidative degradation of the hemp pulp liquid in the subsequent steps is prevented from being aggravated; and after the impregnation is finished, performing a secondary pressing step.

The method comprises the following steps of (1) secondary squeezing, wherein the secondary squeezing temperature is 70-85 ℃, and the squeezing multiple is 1.6-1.8, in the secondary squeezing, residual hydrogen peroxide, alkali liquor and hemicellulose can be removed through rapid squeezing, meanwhile, the content of α -cellulose in the fibrilia is further improved, the reaction performance is improved, in the common squeezing, the squeezing multiple is 2.2-2.5, in the step, the squeezing multiple is obviously reduced, the energy consumption and the time are reduced, and the method is just benefited by the cellulose activation step in the previous stage and the addition of an auxiliary agent in impregnation;

after the secondary pressing, the content of α -cellulose in the pulp is 28-30%, the content of NaOH in percentage by weight is 11-12%, and the concentration of hemicellulose in alkali liquor is less than or equal to 6g/L, the content of hemicellulose in the pulp is obviously reduced through the secondary pressing, the purity of α fiber is further improved, so that the fiber strength is improved, meanwhile, the adding amount of carbon disulfide in the yellowing step can be greatly reduced, the cost is reduced, the average cost per ton is reduced by about 3000 plus 5000 yuan, and the purity of α cellulose in the pulp after pressing is improved by 3-5% compared with that of common alkali cellulose through the process combination.

After secondary pressing, the steps of crushing, ageing and dissolving in alkali liquor are carried out;

the aging step in the step (1) is carried out, wherein the aging temperature is 25-30 ℃, the aging time is 2.5-3 hours, and the polymerization degree of the fiber after polymerization reduction is controlled to be 400-500; the ageing is a long-time process step in the traditional cellulose fiber process; in the invention, the cellulose activation step is carried out at the initial stage of the process, so that the aging time is reduced, the production efficiency is improved, the efficiency is improved by more than 20 percent compared with the common production process, and meanwhile, the aging time is shortened, so that the process adjustment is matched, and the damage to fibrilia is reduced; after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali solution, the concentration of the alkali solution is 150-170 g/L;

in the step (2), the preparation step of the hemp pulp cellulose sulfonate solution comprises the steps of adding 22-24% of carbon disulfide to α -cellulose content in aged alkali cellulose, further improving the purity of α fiber, greatly reducing the adding amount of carbon disulfide in the yellowing step, reducing the cost by about 5-10%, controlling the reaction time for 35-45min in the preparation step of the cellulose sulfonate solution, controlling the initial temperature for 21-24 ℃ in the preparation step of the cellulose sulfonate solution, and controlling the terminal temperature for 25-27 ℃ in the preparation step of the cellulose sulfonate solution.

In the reaction process of carbon disulfide and alkali cellulose, if the yellowing temperature rises, the yellowing reaction is accelerated, the cellulose oxidative cracking speed is accelerated, and the polymerization degree is obviously reduced, so that proper temperature and time need to be controlled;

in the step (3), the silk fibroin solution is prepared by the following steps:

a. boiling: placing silk in a pot with a temperature of 85-90 deg.C, and boiling for 10-20 min; and after the boiling is finished, clockwise stirring for 5-10min, and due to high temperature, the spatial structure of the protein can be denatured, but the surface colloid of the silk is not damaged, only the structure of the silk is loosened, and the silk is taken out.

b. Cutting the extracted fibroin tows into pieces smaller than 10 mm;

c. putting the silk protein tow fragments into a dissolving solution with the mass of 4-5 times of that of the silk protein, and stirring and dissolving for 3-5 min; the dissolving solution consists of sodium hydroxide, vitamin C, an auxiliary agent and water; in the dissolving solution, the mass ratio of sodium hydroxide, vitamin C, auxiliary agent and water is 15-30:5-10:8-15: 100-150; the dissolving liquid can improve the dissolving speed, and the dissolving efficiency is improved by 30-50%; meanwhile, the emulsion can be prevented from yellowing, the whiteness of the fiber can be improved, and the whiteness can be improved by 10-15 degrees.

The auxiliary agent comprises the following components: propanol, Roman chamomile hydrosol and seaweed gel; the auxiliary agent comprises the following components in parts by weight: 10-15 parts of propanol, 5-8 parts of Roman chamomile hydrosol and 1-3 parts of seaweed gel;

the auxiliary agent can improve the dispersion uniformity of each component and the stability of the emulsion; meanwhile, the vitamin C can be prevented from being oxidized in an alkaline environment; the dissolving speed is improved, and the dissolving efficiency is improved by 30-50%; in addition, the Roman chamomile and seaweed gel are compounded to increase the moisture retention of the skin, so that the moisture retention effect of the skin of a human body is increased, and the Roman chamomile and the seaweed gel are matched with the fibroin to further lock the moisture of the skin, supplement the lacked collagen and have an obvious repairing effect on skin acnes; the fibroin regenerated cellulose fiber is added into the preparation of the facial mask to prepare the protein facial mask, which is an important innovation.

The preparation method of the dissolving solution in the step c comprises the following steps: firstly, dissolving sodium hydroxide in water, wherein the sodium hydroxide is dissolved into exothermic reaction, so that the temperature of water is raised to 75-90 ℃, and the pH value is 10-12; then adding vitamin C into the solution, and rapidly stirring and dissolving within 30 s; slowly adding fibroin tow pieces into the solution, and stirring for dissolving for 3-5 min; after the dissolution is finished, rapidly cooling to 3-5 ℃, preventing the oxidation of the vitamin and keeping as much vitamin C as possible; then adding an auxiliary agent, and uniformly shaking to prepare a silk fibroin solution;

heating the prepared silk fibroin solution to 50-60 ℃, concentrating to 2 times of the mass of silk fibroin tow fragments, and preparing into concentrated solution;

adding the prepared concentrated solution into the hemp pulp cellulose sulfonate solution prepared in the step (3) to prepare spinning solution; the addition amount of the concentrated solution is 15-20% of the mass of the hemp pulp cellulose sulfonate solution; after concentration, the concentrated solution is beneficial to being added into a jute pulp cellulose sulfonate solution, the strength of the fiber is not reduced after the fiber is prepared, and the characteristics of the prepared fibroin regenerated cellulose fiber are ensured;

filtering and defoaming the spinning solution obtained in the step (4), and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is less than or equal to-0.1 Mpa;

the filtration in the step (4) adopts a three-way filtration mode, the aperture of a first-way filtration filter screen is 25 mu m, and ions and mechanical impurities are removed; removing micro-particle particles from the second filter screen with the aperture of 10 mu m; the aperture of the three filter screens is 8 mu m, so that the newly added impurities are prevented from blocking a spinning nozzle;

the spinning solution enters a spinneret assembly after passing through a curved tube and a filter, and the spinning solution forms tows through the spinneret assembly and enters a spinning bath; in order to further improve the breaking strength of the prepared fibroin regenerated cellulose fiber and improve the softness of the fiber, the spinning bath is reset; the spinning bath is divided into a first bath, a second bath and a third bath;

the one-bath composition comprises: 40-70g/l of sulfuric acid, 220-260g/l of sodium sulfate and one bath temperature of 30-50 ℃; the drawing rate after one bath is 20-30%;

the two bath components comprise sulfuric acid with the concentration of 50-80 g/l; the drafting rate after the second bath is 70-90%; the temperature of the second bath is 60-70 ℃;

the three bath components comprise 10-20 g/l; the drafting rate after three baths is 20-30%, and the temperature of the three baths is 60-70 ℃;

through the adjusted drafting, zinc sulfate is removed, so that zinc-free spinning is realized, the environmental protection pressure is reduced, meanwhile, the component content, the temperature and the drafting rate of the first bath, the second bath and the third bath are adjusted, the crystal structure of the fiber is changed, the breaking strength of the fiber is greatly improved, and the softness of the fiber is improved;

in the second bath, a denaturant is preferably added; the denaturant is one or more of LS-6 and HB-652;

the denaturant is produced by Shenyang Haobo industry Co.Ltd; the concentration of the denaturant in the acid bath is 10-25 mg/L; the denaturant can reduce the interfacial tension of the viscose and the solution, disperse the precipitate mainly containing sulfur in the spinning bath, reduce the scaling and the blockage of a spinning nozzle, prolong the period of changing the spinning head, improve the spinnability and reduce the rate of changing the spinning head by 10 to 20 percent; meanwhile, the luster of the fiber can be greatly improved, and the prepared fiber has a silky feeling by being matched with the fibroin.

In the post-treatment step in the step (4), a sodium sulfite solution with weak alkalinity is adopted when refining desulfurization treatment is carried out, the concentration is 11-13g/l, and the temperature is 70-85 ℃; the sodium sulfite can prevent the fiber from being oxidized, and can prevent the problem that the generated ferrous sulfide is difficult to remove when sodium sulfide is generally used as a desulfurizing agent.

Bleaching with 1-1.5g/l hydrogen peroxide at 70-75 deg.C, and maintaining pH at 8-10;

in the bleaching process, preferably adding a buffer of water glass and soap liquid; the concentration of the water glass is 0.5-1.5g/L, and the concentration of the soap liquid is 0.03-0.1%; can prevent cellulose macromolecules from being oxidized and improve the strength of the fiber;

the post-treatment in the step (4) further comprises a drying process: the moisture content of the fibers after being subjected to water pricking is kept at 100-; proper temperature is adopted for drying, and the temperature of the front drying zone is 60-80 ℃; the temperature in drying is 75-90 ℃; the temperature of the dried area is 60-70 ℃; the prepared fibroin cellulose fiber is ensured not to become brittle and yellow, and the silk composite cellulose fiber is prepared.

Due to the adoption of the technical scheme, the invention achieves the technical effects that:

1. the invention adopts the specific hemp pulp as the main raw material, not only can enable the prepared fiber to have the antibacterial property of the hemp natural fiber, but also endows the fiber with better glossiness and moisture absorption and air permeability, greatly improves the glossiness of the fiber, and enables the prepared fiber to have silk-like feeling by matching with the fibroin;

2. the protein content in the silk protein fiber prepared by the invention is more than or equal to 5 percent, and because the fiber contains a large amount of protein amino acid, the silk protein fiber can supplement protein lacking in skin, and simultaneously the moisturizing effect is enhanced, so that the silk protein fiber is preferable for preparing facial masks and underwear;

3. the protein content of the fibroin fiber prepared by the invention is more than or equal to 5 percent, the amorphous region of the fibroin fiber is combined with the cellulose, the breaking strength of the cellulose fiber can be improved, generally, the wet breaking strength of the cellulose fiber is not high, but the wet breaking strength of the fibroin regenerated cellulose fiber is more than or equal to 1.9 cN/dtex;

4. the facial mask prepared by the invention is not easy to tear, and can form good fit on the face; the manufactured underwear has good comfort and wrapping property;

5. the method has the steps of activating cellulose in the process of preparing the fibroin; adding hydrogen peroxide in the degradation step; the hydrogen peroxide has slow and moderate oxidation performance, on one hand, the hemicellulose, ash, tannin and colloid in the hemp pulp fiber are removed, on the other hand, the hydrogen peroxide slowly releases gas, the capillary space between the fibers is increased, so that the fibers are fully filled with micro bubbles, and the impregnation uniformity and the reaction performance of the hemp pulp are improved;

6. according to the invention, water and hydrogen peroxide in the cellulose activation step are squeezed out through one-time squeezing, the hydrogen peroxide increases the space between fibrilia, a vacuum state is formed between the fibers after squeezing, and alkali liquor is easy to permeate and impregnate in the subsequent impregnation step, so that the impregnation uniformity is further improved;

7. in the dipping process, the auxiliary agent liquid is required to be added into the dipping liquid, so that the reaction performance of the slurry is further improved, and excessive degradation of the hemp slurry in the subsequent steps is prevented;

8. in the process of the invention, the secondary pressing multiple is obviously reduced, the efficiency is improved, and the energy consumption is reduced;

9. the method has the advantages that the content of hemicellulose in the alkali cellulose is obviously reduced through twice squeezing, the purity of α fiber is further improved, the strength of the fiber is improved, the addition amount of carbon disulfide in the yellowing step can be greatly reduced, the cost is reduced by about 3000-5000 yuan, and the purity of α cellulose in the alkali cellulose is improved by 3-5% compared with that of common alkali cellulose through twice squeezing and related procedures;

10. the invention carries out the step of activating the cellulose in the initial stage of the process, thereby reducing the aging time, improving the production efficiency by more than 20 percent compared with the common production process;

11. because the purity of α -cellulose in the alkali cellulose is improved, the addition amount of carbon disulfide in the yellowing step is greatly reduced, and the cost is reduced by about 5-10%;

12. in the process of the invention, the preparation of the silk fibroin solution reserves the colloid on the surface of the silk, and the colloid on the surface of the silk can be combined with fiber molecules in the fiber amorphous region during fiber forming, thereby further improving the strength of the fiber;

13. in the process of the invention, the solution prepared from the silk fibroin solution can improve the dissolving speed and improve the dissolving efficiency by 30-50%;

14. in the process of the invention, the solution prepared from the silk fibroin solution can prevent the emulsion from yellowing, improve the whiteness of the fiber, and improve the whiteness by 10-15 ℃;

15. in the process of preparing the silk fibroin solution, the prepared solution comprises an auxiliary agent; the addition of the auxiliary agent can improve the dispersion uniformity of each component and the stability of the emulsion; meanwhile, the vitamin C can be prevented from being oxidized in an alkaline environment; the dissolving speed is improved, and the dissolving efficiency is improved by 30-50%; in addition, the Roman chamomile and seaweed gel are compounded to increase the moisture retention of the skin, so that the moisture retention effect of the skin of a human body is increased, and the Roman chamomile and the seaweed gel are matched with the fibroin to further lock the moisture of the skin, supplement the lacked collagen and have an obvious repairing effect on skin acnes; the fibroin regenerated cellulose fiber is added into the preparation of the facial mask to prepare the protein facial mask, which is an important innovation;

16. in the process of preparing the fibroin regenerated cellulose fiber, a zinc-free three-bath method is adopted, so that the breaking strength of the prepared fibroin regenerated cellulose fiber is further improved;

17. in the invention, in the second bath, a denaturant is added; the interfacial tension of the viscose and the solution is reduced, the precipitate mainly containing sulfur in the spinning bath is dispersed, the scaling and the blockage of a spinning nozzle are reduced, the head changing period is prolonged, the spinnability is improved, and the head changing rate of the spinning nozzle is reduced by 10-20%.

Detailed Description

The purpose, technical solution and advantageous effects of the present invention will be described in further detail below.

It is to be understood that the following detailed description is exemplary rather than a comprehensive description, and that all technical terms and units used herein are understood by those skilled in the art unless otherwise specified; the following examples are provided to illustrate specific embodiments of the present invention, and it is understood that the scope of the present invention is not limited to the following examples.

The index detection method of the invention comprises the following steps:

the whiteness is measured by FZ/T50013; the method for measuring the radial water swelling degree is GB/T6503; fiber crystallinity determination method: measuring by adopting an infrared spectroscopy; the determination of the dry elongation at break is GB/T14337; the wet elongation at break was determined by GB/T14337; the dry breaking strength is determined by GB/T14337; the wet breaking strength was determined by GB/T14337; the strength required to give 5% elongation in the wet state is achieved by GB/T14337; the linear density deviation ratio is measured by GB/T14335; the residual sulfur was determined by FZ/T50014; the method for measuring the defects is GB/T14339, and the method for measuring the whiteness is FZ/T50013; the measuring method of the ultra-long fiber rate is GB/T14336; the measuring method of the double-length fiber is GB/T14336; the length deviation ratio is measured in GB/T14336.

Example 1

The fibroin regenerated cellulose fiber prepared by the invention has the following relevant indexes:

dry breaking strength 3.2cN/dtex, wet breaking strength 1.9 cN/dtex;

the fibroin content is 6%;

dry elongation at break of 13.5% and wet elongation at break of 18.5%;

the crystallinity is 41 percent, and the radial water swelling degree is 25 percent;

the fineness deviation rate is 1.3 percent, and the residual sulfur content is 3mg/100 g;

fiber defects of 0.4mg/100g and long fiber rate of 0.2 percent;

the length-doubled fiber is 0.5mg/100mg, and the length deviation rate is 1%;

the whiteness is 82%.

Example 2

This example differs from example 1 in that: the fibroin regenerated cellulose fiber prepared by the invention has the following relevant indexes: dry breaking strength 3.4cN/dtex, wet breaking strength 2.1 cN/dtex;

the fibroin content is 5%;

dry elongation at break of 13.1% and wet elongation at break of 17.9%;

the crystallinity is 42 percent, and the radial water swelling degree is 30 percent;

the fineness deviation rate is 1.5 percent, and the residual sulfur content is 4mg/100 g;

the fiber defect is 0.3mg/100g, and the long fiber rate is 0.1%;

the length-doubled fiber is 0.3mg/100mg, and the length deviation rate is 2 percent;

the whiteness is 83 percent.

Example 3

The process method for regenerating the cellulose fiber by the fibroin related by the embodiment specifically comprises the following steps:

(1) the hemp pulp is prepared into hemp pulp after pre-crushing, cellulose activation, primary pressing, alkali liquor impregnation, secondary pressing, crushing and alkali liquor dissolution;

Example 4

This example differs from example 3 in that: in the preparation method of the fibroin regenerated cellulose fiber according to the embodiment, the adopted hemp pulp raw material has the following indexes:

the polymerization degree is 500, and the ash content is 0.5%;

α -cellulose content 93-%, alkali absorption value 550%;

the swelling degree (volume) is 300 percent, and the water content is 8.4 percent;

dust particle of 40mm²Per kg, 0.2 big dust per kg;

the iron content is 10mg/kg, and the ash content is 0.02%;

reactivity 22s, esterThe content of fatty wax is 0.1 percent, and the definite volume weight is 350g/m³。

Example 5

the polymerization degree is 600, and the ash content is 0.6%;

α -cellulose content 96%, alkali absorption value 600%;

the swelling degree (volume) is 350 percent, and the water content is 9.5 percent;

small dust 32mm²Per kg, 0.5 dust per kg;

the iron content is 13mg/kg, and the ash content is 0.03%;

the reaction performance is 70s, the content of the fatty wax is 0.1 percent, and the definite volume weight is 500g/m³。

Example 6

This example differs from example 3 in that: in the cellulose activation step according to the present example, hydrogen peroxide was added to the pulverized slurry; the concentration of the hydrogen peroxide in the slurry is 15 g/L; the slurry is heated to 40 ℃ in the slurry pool, and the stirring is circulated for 30min, so that the activation of the fiber in the slurry can be realized.

Example 7

This example differs from example 3 in that: in the cellulose activation step according to the present example, hydrogen peroxide was added to the pulverized slurry; the concentration of the hydrogen peroxide in the slurry is 20 g/L; the slurry is heated to 55 ℃ in the slurry pool, and the stirring is circulated for 40min, so that the activation of the fiber in the slurry can be realized.

Example 8

This example differs from example 6 in that: in the step of activating the cellulose, an activating agent dz-01 is added into the slurry; the concentration of the activating agent dz-01 in the slurry was made to be 1 g/L.

Example 9

This example differs from example 7 in that: in the step of activating the cellulose, adding an activating agent dz-01 into the slurry; the concentration of the activating agent dz-01 in the slurry was made to be 2 g/L.

Example 10

This example differs from example 3 in that: in the primary pressing step according to this example, the primary pressing temperature was 25 ℃ and the pressing factor was 2.

Example 11

This example differs from example 3 in that: in the primary pressing step according to this example, the primary pressing temperature was 30 ℃ and the pressing factor was 2.3.

Example 12

This example differs from example 3 in that: the lye impregnation step referred to in this example: soaking the hemp pulp after primary pressing in NaOH soaking liquid with the concentration of 100g/l, wherein the soaking temperature is 20 ℃, the soaking time is 30 minutes, and the hemicellulose concentration of the soaking liquid is less than 20 g/l.

Example 13

This example differs from example 3 in that: the lye impregnation step referred to in this example: soaking the hemp pulp subjected to primary pressing in NaOH soaking solution with the concentration of 140g/l, wherein the soaking temperature is 30 ℃, the soaking time is 50 minutes, and the hemicellulose concentration of the soaking solution is less than 20 g/l.

Example 14

This example differs from example 3 in that: in the step of alkali liquor impregnation in this embodiment, an additive liquid needs to be added, and the addition amount of the additive liquid is 2% of the impregnation alkali liquor; the auxiliary liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water; OS-406, a high molecular weight polyether surfactant solution having a pH of 7, an HLB of 17, a viscosity of 600 mPa.S (25 ℃), a surface tension of 20 mN/m; the auxiliary agent liquid comprises the following components in parts by weight: 2 parts of OS-406, 0.8 part of dibutyl hydroxy toluene, 3 parts of ethanol, 1 part of sodium carbonate and 40 parts of deionized water.

Example 15

This example differs from example 3 in that: in the step of alkali liquor impregnation in this embodiment, an additive liquid needs to be added, and the addition amount of the additive liquid is 4% of the impregnation alkali liquor; the auxiliary agent liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water; OS-406, a high molecular weight polyether surfactant solution having a pH of 9, an HLB of 18, a viscosity of 800 mPa.S (25 ℃), a surface tension of 23 mN/m; the auxiliary agent liquid comprises the following components in parts by weight: 2 parts of OS-406, 0.8 part of dibutyl hydroxy toluene, 4 parts of ethanol, 1 part of sodium carbonate and 40-50 parts of deionized water.

Example 16

A preparation method of fibroin regenerated cellulose fiber comprises the following steps:

In the step (1), the hemp pulp raw material has the relevant indexes of 550 percent of polymerization degree, 0.3 percent of ash content, α -cellulose content of 95 percent, 550 percent of alkali absorption value, 300 percent of swelling degree (volume), 8.5 +/-1.0 percent of water content and 80mm of small dust²0.3 dust/kg, 15mg/kg iron content, less than or equal to 0.02 percent of ash content, 25s of reactivity, 0.05 percent of fatty wax content and 300g/m of definite volume weight³。

The hemp pulp is jute; the hemp pulp can endow the fiber with better antibacterial property, glossiness and moisture absorption and air permeability;

in the step (1), a pre-crushing step, namely crushing the hemp pulp into slurry by adopting a crusher, wherein the crushing degree is 350 g/L; the slurry with proper concentration is crushed, the reaction surface area is increased, the production efficiency is improved, and necessary conditions are provided for subsequent processes;

in the step (1), the cellulose activation step: adding hydrogen peroxide into the crushed slurry; the concentration of the hydrogen peroxide in the slurry is 20 g/L; heating the slurry to 40 ℃ in a slurry pool, and stirring and circulating for 30 min; the hydrogen peroxide has slow and moderate oxidation performance, on one hand, hemicellulose, ash, tannin and colloid in a small part of the hemp pulp fiber are removed, on the other hand, the hydrogen peroxide slowly releases bubbles to attach to the surface of the hemp fiber, the capillary space between the fibers is increased, so that the fibers are filled with micro bubbles, the impregnation uniformity and the reaction performance of the hemp pulp are improved, and the color fastness to washing of the fiber product is further improved; after being activated by cellulose, the jute pulp has 500 polymerization degree.

In the step of activating the cellulose, an activating agent dz-01 is added, the concentration of the activating agent in the pulp is 1g/L, α -cellulose in the hemp pulp can be protected from being degraded by hydrogen peroxide, and the bleaching effect of the hydrogen peroxide is avoided as much as possible

In the step (1), in the primary squeezing step, the primary squeezing temperature is 25 ℃, and the squeezing multiple is 2.3 times; can extrude moisture and hydrogen peroxide in the cellulose activation step, hydrogen peroxide content is lower, therefore the liquid of extruding can recycle, simultaneously behind the cellulose activation step, hydrogen peroxide has increased the interval between the fibrilia, after squeezing, forms "vacuum" state between the fibre, in follow-up impregnation step, alkali lye is very easy to permeate and impregnate, further improves the degree of consistency of impregnating.

Step (1), an alkali liquor dipping step, wherein the hemp pulp is dipped in NaOH dipping solution with the concentration of 100g/l to carry out alkalization reaction, the dipping temperature is 20 ℃, the dipping time is 30 minutes, the hemicellulose concentration of the dipping solution is less than 20g/l, and the dipped alkali cellulose enters a secondary squeezing step;

adding an auxiliary agent solution into the impregnation solution, wherein the addition amount of the auxiliary agent solution is 2% of the impregnation alkali solution; the reaction performance of the pulp is further improved, and the degradation of the hemp pulp in the subsequent steps is reduced; compared with cotton pulp and wood pulp, the polymerization degree of the hemp pulp is easier to degrade after reaching certain conditions; if the cellulose activation is carried out in the early stage without control, the hemp pulp is degraded too violently in the subsequent steps, and finally the fiber strength is lower;

the auxiliary liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;

OS-406, a high molecular weight polyether surfactant solution having a pH of 8, an HLB of 17, a viscosity of 700 mPa.S (25 ℃), a surface tension of 21 mN/m;

in the auxiliary agent liquid, the components are specifically as follows according to parts by weight: 3 parts of OS-406, 1 part of dibutyl hydroxy toluene, 5 parts of ethanol, 1 part of sodium carbonate and 40 parts of deionized water.

The addition of the auxiliary agent liquid further improves the reaction performance of the slurry, and the reaction performance can be improved by 5-10%; meanwhile, the oxidative degradation of the hemp pulp liquid in the subsequent steps is prevented from being aggravated; and after the impregnation is finished, performing a secondary pressing step.

In the secondary squeezing step of the step (1), the secondary squeezing temperature is 75 ℃, and the squeezing multiple is 1.6, in the secondary squeezing step, the residual hydrogen peroxide, alkali liquor and hemicellulose can be removed by rapid squeezing, and meanwhile, the content of α -cellulose in the fibrilia is further improved, and the reaction performance is improved;

after the secondary pressing, the content of α -cellulose in the alkali cellulose is 28%, the content of NaOH in percentage by weight is 11%, and the concentration of hemicellulose in alkali liquor is 5g/L, the invention obviously reduces the content of hemicellulose in the alkali cellulose through the secondary pressing, further improves the purity of α fiber, improves the fiber strength, can greatly reduce the addition of carbon disulfide in the yellowing step, reduces the cost, reduces the average cost per ton by about 3000 plus 5000 yuan, and improves the purity of α cellulose in the alkali cellulose by 3-5% compared with the common alkali cellulose through the process combination.

an ageing step in the step (1), wherein the ageing temperature is 26 ℃, the ageing time is 2.5 hours, and the degree of polymerization of the fibers after the polymerization is reduced is controlled to be 400;

after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali liquor solution, the concentration of the alkali liquor is 150 g/L;

in the step (2), the preparation step of the hemp pulp cellulose sulfonate solution comprises the steps of adding carbon disulfide into the aged alkali cellulose in an amount which is 22 percent of the content of α -cellulose, controlling the reaction time for 35min in the preparation step of the cellulose sulfonate solution, controlling the initial temperature to be 24 ℃ in the preparation step of the cellulose sulfonate solution and controlling the terminal temperature to be 25 ℃ in the preparation step of the cellulose sulfonate solution.

In the step (3), the silk fibroin solution is prepared by the following steps:

a. boiling: placing silk in a pot with a temperature of about 85 deg.C, and boiling for 10 min; after the boiling is finished, clockwise stirring is carried out for 5min, due to high temperature, the protein space structure can be denatured, but the silk surface colloid is not damaged, only the silk structure is loosened, and the silk is taken out.

b. Cutting the extracted silk protein tows into 5mm fragments;

c. putting the silk protein tow fragments into a dissolving solution with the mass of 4 times of that of the silk protein, and stirring and dissolving for 3 min; the dissolving solution consists of sodium hydroxide, vitamin C, an auxiliary agent and water; in the dissolving solution, the mass ratio of sodium hydroxide, vitamin C, an auxiliary agent and water is 15:7:8: 100;

the auxiliary agent comprises the following components: propanol, Roman chamomile hydrosol and seaweed gel; the auxiliary agent comprises the following components in parts by weight: 10 parts of propanol, 6 parts of Roman chamomile hydrosol and 1 part of seaweed gel;

the preparation method of the dissolving solution in the step c comprises the following steps: firstly, dissolving sodium hydroxide in water, wherein the sodium hydroxide is dissolved into exothermic reaction, and the temperature of water is raised to the required temperature, and the pH value is 10; then adding vitamin C into the solution, and rapidly stirring and dissolving within 30 s; slowly adding fibroin tow pieces into the solution, and stirring for dissolving for 3 min; after the dissolution is finished, rapidly cooling to 5 ℃, preventing the oxidation of the vitamin and keeping as much vitamin C as possible; then adding an auxiliary agent, and uniformly shaking to prepare a silk fibroin solution;

heating the prepared silk fibroin solution to 50 ℃, concentrating the solution until the mass of the silk fibroin fragments is 2 times that of the silk fibroin silk bundle fragments, and preparing a concentrated solution;

adding the prepared concentrated solution into the hemp pulp cellulose sulfonate solution prepared in the step (3) to prepare spinning solution; the adding amount of the concentrated solution is 15 percent of the mass of the hemp pulp cellulose sulfonate solution;

filtering and defoaming the spinning solution in the step (4), and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is-0.1 Mpa;

the spinning solution enters a spinneret assembly after passing through a curved tube and a filter, and the spinning solution forms tows through the spinneret assembly and enters a spinning bath; the spinning bath is divided into a first bath, a second bath and a third bath;

one bath composition comprises: 40g/l of sulfuric acid, 220g/l of sodium sulfate and 30 ℃ of one bath temperature; the drawing rate after one bath is 20 percent;

the second bath component comprises sulfuric acid with the concentration of 50 g/l; the draft ratio after the second bath is 70 percent; the temperature of the second bath is 60 ℃;

the three bath components comprise 10 g/l; the drafting rate after three baths is 20 percent, and the temperature of the three baths is 60 ℃;

in the second bath, a denaturant is added; the denaturant is LS-6;

the concentration of the denaturant in the acid bath is 10 mg/L;

in the post-treatment step in the step (4), a sodium sulfite solution with weak alkalinity is adopted when refining desulfurization treatment is carried out, the concentration is 11g/l, and the temperature is 70 ℃; the sodium sulfite can prevent the fiber from being oxidized, and can prevent the problem that the generated ferrous sulfide is difficult to remove when sodium sulfide is generally used as a desulfurizing agent.

Bleaching with 1g/l hydrogen peroxide at 70 deg.c and pH of 8;

in the bleaching process, preferably adding a buffer of water glass and soap liquid; the concentration of the water glass is 0.5g/L, and the concentration of the soap liquid is 0.03-0.1%; can prevent cellulose macromolecules from being oxidized and improve the strength of the fiber;

the post-treatment in the step (4) further comprises a drying process: the moisture content of the fibers after being subjected to water pricking is kept at 100%, and the fibers are opened in the drying process, so that the drying uniformity is improved; proper temperature is adopted for drying, and the temperature of the front drying zone is 60 ℃; the temperature in drying is 75 ℃; the temperature of the drying area is 60 ℃; the prepared fibroin cellulose fiber is ensured not to become brittle and yellow, and the silk composite cellulose fiber is prepared.

Example 17

In the step (1), the hemp pulp raw material adopts the relevant indexes that the adopted hemp pulp is kenaf, the polymerization degree is 600, the ash content is 0.2 percent, the α -cellulose content is 96 percent, the alkali absorption value is 550 percent, the swelling degree (volume) is 350 percent, the water content is 8.5 percent, and the dust is 35mm²Per kg, 0.1 dust, 10mg/kg iron content, 0.02% ash content, 20s reactivity, 0.1% fatty wax content, and 300g/m fixed volume weight³。

In the step (1), a pre-crushing step, namely crushing the hemp pulp into slurry by adopting a crusher, wherein the crushing degree is 400 g/L;

in the step (1), the cellulose activation step: adding hydrogen peroxide into the crushed slurry; the concentration of the hydrogen peroxide in the slurry is 20 g/L; heating the slurry to 55 ℃ in a slurry pool, and stirring and circulating for 40 min; after being activated by cellulose, the jute pulp has the polymerization degree of 450.

In the step of activating the cellulose, adding an activating agent dz-01; the concentration of the activating agent in the slurry is 1 g/L; is the activating agent dz-01;

in the step (1), in the primary squeezing step, the primary squeezing temperature is 30 ℃, and the squeezing multiple is 2.3 times;

step (1), an alkali liquor dipping step, wherein the hemp pulp is dipped in NaOH dipping solution with the concentration of 140g/l, the dipping temperature is 30 ℃, the dipping time is 30 minutes, the hemicellulose concentration of the dipping solution is less than 20g/l, and the dipped alkali cellulose enters a secondary squeezing step;

adding an auxiliary agent solution into the impregnation solution, wherein the addition amount of the auxiliary agent solution is 2% of that of the impregnation alkali solution;

OS-406, a high molecular weight polyether surfactant solution having a pH of 8, an HLB of 17, a viscosity of 600 mPa.S (25 ℃), a surface tension of 21 mN/m;

in the auxiliary agent liquid, the components are specifically as follows according to parts by weight: 2 parts of OS-406, 0.8 part of dibutyl hydroxy toluene, 4 parts of ethanol, 3 parts of sodium carbonate and 45 parts of deionized water.

The addition of the auxiliary agent liquid further improves the reaction performance of the pulp, and the reaction performance can be improved by 5%; meanwhile, the oxidative degradation of the hemp pulp liquid in the subsequent steps is prevented from being aggravated; and after the impregnation is finished, performing a secondary pressing step.

Step (1), a secondary squeezing step, wherein the secondary squeezing temperature is 76 ℃, and the squeezing multiple is 1.6;

after secondary pressing, the α -cellulose content in the alkali cellulose is 28 percent, the weight percentage content of NaOH is 12 percent, and the hemicellulose concentration in alkali liquor is 4 g/L;

an ageing step in the step (1), wherein the ageing temperature is 25 ℃, the ageing time is 2.5 hours, and the degree of polymerization of the fibers after the polymerization is reduced is controlled to be 500;

in the step (2), the preparation step of the hemp pulp cellulose sulfonate solution comprises the steps of adding carbon disulfide 23% of α -cellulose content in the aged alkali cellulose, controlling the reaction time for 38min in the preparation step of the cellulose sulfonate solution, controlling the initial temperature to be 21 ℃ in the preparation step of the cellulose sulfonate solution and controlling the terminal temperature to be 25-27 ℃ in the preparation step of the cellulose sulfonate solution.

In the step (3), the silk fibroin solution is prepared by the following steps:

a. boiling: placing silk in a pot with a temperature of about 90 deg.C, and boiling for 20 min; after the boiling is finished, clockwise stirring is carried out for 7min, due to high temperature, the protein space structure can be denatured, but the silk surface colloid is not damaged, only the silk structure is loosened, and the silk is taken out.

b. Cutting the extracted silk protein tows into 6mm fragments;

c. putting the silk protein tow fragments into a dissolving solution with the mass of 4 times of that of the silk protein, and stirring and dissolving for 5 min; the dissolving solution consists of sodium hydroxide, vitamin C, an auxiliary agent and water; in the dissolving solution, the mass ratio of sodium hydroxide, vitamin C, an auxiliary agent and water is 20:7:8: 150;

the auxiliary agent comprises the following components: propanol, Roman chamomile hydrosol and seaweed gel; the auxiliary agent comprises the following components in parts by weight: 12 parts of propanol, 5 parts of Roman chamomile hydrosol and 3 parts of seaweed gel;

the preparation method of the dissolving solution in the step c comprises the following steps: firstly, dissolving sodium hydroxide in water, wherein the sodium hydroxide is dissolved into exothermic reaction, and the temperature of water is raised to the required temperature, and the pH value is 12; then adding vitamin C into the solution, and rapidly stirring and dissolving within 30 s; slowly adding fibroin tow pieces into the solution, and stirring for dissolving for 3 min; after the dissolution is finished, rapidly cooling to 5 ℃, preventing the oxidation of the vitamin and keeping as much vitamin C as possible; then adding an auxiliary agent, and uniformly shaking to prepare a silk fibroin solution;

the one-bath composition comprises: 52g/l of sulfuric acid, 235g/l of sodium sulfate and 32 ℃ of one bath temperature; the drawing rate after one bath is 20 percent;

the two bath components comprise sulfuric acid with the concentration of 65 g/l; the draft ratio after the second bath is 70 percent; the temperature of the second bath is 70 ℃;

the three bath components comprise 20 g/l; the drafting rate after three baths is 23 percent, and the temperature of the three baths is 65 ℃;

in the second bath, a denaturant is added; the denaturant is HB-652;

the concentration of the denaturant in the acid bath is 25 mg/L;

in the post-treatment step in the step (4), sodium sulfite solution with weak alkalinity is adopted when refining desulfurization treatment is carried out, the concentration is 13g/l, and the temperature is 85 ℃;

bleaching with 1g/l hydrogen peroxide at 75 deg.c and pH of 8;

in the bleaching process, adding a buffering agent, namely water glass and soap liquid; the concentration of the water glass is 1.5g/L, and the concentration of the soap liquid is 0.031%;

the post-treatment in the step (4) further comprises a drying process: the moisture content of the fibers after being subjected to water pricking is kept at 100%, and the fibers are opened in the drying process, so that the drying uniformity is improved; proper temperature is adopted for drying, and the temperature of the drying front zone is 80 ℃; the temperature in drying is 78 ℃; the temperature of the drying area is 65 ℃; the prepared fibroin cellulose fiber is ensured not to become brittle and yellow, and the silk composite cellulose fiber is prepared.

Example 18

In the step (1), the hemp pulp raw material has the relevant indexes of 600 percent of polymerization degree, 0.1 percent of ash content, α -96 percent of cellulose content, 600 percent of alkali absorption value, 50 percent of swelling degree (volume), 8.5 percent of water content and 25mm of small dust²Per kg, 0.1 dust, 5mg/kg iron, 0.02% ash, 18s reaction performance, 0.1% fatty wax, 300g/m fixed volume weight³。

The hemp pulp is jute; in the step (1), a pre-crushing step, namely crushing the hemp pulp into slurry by adopting a crusher, wherein the crushing degree is 375 g/L;

in the step (1), the cellulose activation step: adding hydrogen peroxide into the crushed slurry; the concentration of the hydrogen peroxide in the slurry is 15 g/L; heating the slurry to 50 ℃ in a slurry pool, and stirring and circulating for 30 min; after activation with cellulose, the jute pulp had a degree of polymerization of 475.

In the step of activating the cellulose, adding an activating agent dz-01; the concentration of the activating agent in the slurry is 1 g/L;

in the step (1), in the primary squeezing step, the primary squeezing temperature is 30 ℃, and the squeezing multiple is 2 times;

step (1), an alkali liquor dipping step, wherein the hemp pulp is dipped in NaOH dipping solution with the concentration of 120g/l to carry out alkalization reaction, the dipping temperature is 30 ℃, the dipping time is 45 minutes, the hemicellulose concentration of the dipping solution is less than 20g/l, and the dipped alkali cellulose enters a secondary squeezing step;

adding an auxiliary agent solution into the impregnation solution, wherein the addition amount of the auxiliary agent solution is 3% of the impregnation alkali solution; the reaction performance of the pulp is further improved, and the degradation of the hemp pulp in the subsequent steps is reduced; compared with cotton pulp and wood pulp, the polymerization degree of the hemp pulp is easier to degrade after reaching certain conditions;

OS-406, a high molecular weight polyether surfactant solution having a pH of 8, an HLB of 17, a viscosity of 600 mPa.S (25 ℃), a surface tension of 20 mN/m;

in the auxiliary agent liquid, the components are specifically as follows according to parts by weight: 5 parts of OS-406, 1.2 parts of dibutyl hydroxy toluene, 6 parts of ethanol, 1 part of sodium carbonate and 43 parts of deionized water.

The method comprises the following steps of (1) carrying out secondary squeezing, wherein the secondary squeezing temperature is 80 ℃, and the squeezing multiple is 1.6;

after secondary pressing, the α -cellulose content in the pulp is 28-30%, the weight percentage content of NaOH is 11-12%, and the concentration of hemicellulose in alkali liquor is less than or equal to 6 g/L;

an ageing step in the step (1), wherein the ageing temperature is 25-30 ℃, the ageing time is 2.5 hours, and the degree of polymerization of the fibers after polymerization reduction is controlled to be 400;

after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali solution, the concentration of the alkali solution is 150-170 g/L;

in the step (2), the preparation step of the hemp pulp cellulose sulfonate solution comprises the steps of adding carbon disulfide 23% of α -cellulose content in the aged alkali cellulose, controlling the reaction time for 42min in the preparation step of the cellulose sulfonate solution, controlling the initial temperature to be 21 ℃ in the preparation step of the cellulose sulfonate solution and controlling the terminal temperature to be 27 ℃ in the preparation step of the cellulose sulfonate solution.

In the step (3), the silk fibroin solution is prepared by the following steps:

a. boiling: placing silk in a pot with a temperature of about 90 deg.C, and boiling for 20 min; after the boiling is finished, the mixture is stirred clockwise for 10min, and due to high temperature, the spatial structure of the protein can be denatured, but the colloid on the surface of the silk is not damaged, only the structure of the silk is loosened, and the silk is taken out.

b. Cutting the extracted silk protein tows into 5mm fragments;

c. putting the silk protein tow fragments into a dissolving solution with the mass of 5 times of that of the silk protein, stirring and dissolving for 5 min; the dissolving solution consists of sodium hydroxide, vitamin C, an auxiliary agent and water; in the dissolving solution, the mass ratio of sodium hydroxide, vitamin C, an auxiliary agent and water is 15: 10:8: 120;

the auxiliary agent comprises the following components: propanol, Roman chamomile hydrosol and seaweed gel; the auxiliary agent comprises the following components in parts by weight: 105 parts of propanol, 8 parts of Roman chamomile hydrosol and 3 parts of seaweed gel;

the preparation method of the dissolving solution in the step c comprises the following steps: firstly, dissolving sodium hydroxide in water, wherein the sodium hydroxide is dissolved into an exothermic reaction, and the temperature of water is raised to a required temperature, and the pH value is 11; then adding vitamin C into the solution, and rapidly stirring and dissolving within 30 s; slowly adding fibroin tow pieces into the solution, and stirring for dissolving for 5 min; after the dissolution is finished, rapidly cooling to 3-5 ℃, preventing the oxidation of the vitamin and keeping as much vitamin C as possible; then adding an auxiliary agent, and uniformly shaking to prepare a silk fibroin solution;

adding the prepared concentrated solution into the hemp pulp cellulose sulfonate solution prepared in the step (3) to prepare spinning solution; the adding amount of the concentrated solution is 15 percent of the mass of the hemp pulp cellulose sulfonate solution; after concentration, the concentrated solution is beneficial to being added into a jute pulp cellulose sulfonate solution, the strength of the fiber is not reduced after the fiber is prepared, and the characteristics of the prepared fibroin regenerated cellulose fiber are ensured;

the one-bath composition comprises: 55g/l of sulfuric acid, 240g/l of sodium sulfate and 38 ℃ of one bath temperature; the drawing rate after one bath is 25 percent;

the two bath components comprise sulfuric acid with the concentration of 75 g/l; the draft ratio after the second bath is 70 percent; the temperature of the second bath is 70 ℃;

the three bath components comprise 15 g/l; the drafting rate after three baths is 22 percent, and the temperature of the three baths is 60 ℃;

in the second bath, a denaturant is added; the denaturant is LS-6 and HB-652;

the denaturant is produced by Shenyang Haobo industry Co.Ltd; the concentration of the denaturant in the acid bath is 10-25mg/L, and the concentration of HB-652 is 3-5 g/L;

in the post-treatment step in the step (4), sodium sulfite solution with weak alkalinity is adopted when refining desulfurization treatment is carried out, the concentration is 13g/l, and the temperature is 75 ℃; the sodium sulfite can prevent the fiber from being oxidized, and can prevent the problem that the generated ferrous sulfide is difficult to remove when sodium sulfide is generally used as a desulfurizing agent.

Bleaching with 1.5g/l hydrogen peroxide at 75 deg.c and pH of 8;

in the bleaching process, preferably adding a buffer of water glass and soap liquid; the concentration of the water glass is 0.5g/L, and the concentration of the soap liquid is 0.03%;

the post-treatment in the step (4) further comprises a drying process: the water content of the fibers after being subjected to water binding is kept at 110%, and the fibers are opened in the drying process, so that the drying uniformity is improved; proper temperature is adopted for drying, and the temperature of the front drying zone is 60 ℃; the temperature in drying is 82 ℃; the temperature of the dried area is 65-70 ℃; the prepared fibroin cellulose fiber is ensured not to become brittle and yellow, and the silk composite cellulose fiber is prepared.

The fibroin regenerated cellulose fibers prepared in the examples 1-6, 7-12 and 13-18 of the invention and the fabrics prepared therefrom were tested, and the specific test indexes are shown in Table 1 (corresponding to examples 1-6), Table 2 (corresponding to examples 7-12) and Table 3 (corresponding to examples 13-18)

TABLE 1

TABLE 2

TABLE 3

The index values of the fibroin fibers according to examples 1 to 18 were removed from the maximum and minimum values, and then the average values were calculated, and the calculated average values were compared with modal fibers, ordinary viscose fibers, and application No. 201210387021.4, which is hereinafter referred to as reference 1; the product is a protein cellulose fiber prepared by a method for preparing fibroin blended regenerated cellulose fiber, and a patent with application number of 201110400581.4, wherein the patent name is 'a regenerated animal micro powder protein cellulose fiber and a preparation method thereof', and the product is hereinafter referred to as a comparison document 2; the results of the specific comparisons are shown in Table 4

As can be seen from Table 4, the fibroin cellulose fiber prepared by the method has the fineness of 0.95-1.33D, and can be used for manufacturing facial masks and underwear.

As can be seen from table 4, the dry breaking strength of the fibroin cellulose fiber prepared by the present invention is slightly lower than that of modal fiber, but far higher than that of common viscose fiber; a dry breaking strength of the protein fiber higher than that of the reference; from table 4 it can be seen that the wet breaking strength of the fibroin cellulose fibers prepared by the present invention is almost the same as that of the modal fibers, while the wet breaking strength of the fibroin cellulose fibers prepared in example 18 is already superior to that of the modal fibers, which is an important innovation and improvement.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, the present invention is not limited to the embodiments described above, and various modifications, changes, variations, and alterations may be made without departing from the spirit of the invention.

Claims

1. The application of a silk fibroin solution in the preparation of regenerated cellulose fibers comprises the following steps:

(4) filtering, defoaming, spinning and post-treating the spinning solution to prepare fibroin regenerated cellulose fiber;

in the cellulose activation step, hydrogen peroxide and an activating agent dz-01 are added into the slurry; the concentration of the activating agent dz-01 in the slurry is 1-2 g/L;

the alkali liquor dipping step: soaking the hemp pulp in 140g/l NaOH soaking solution with the concentration of 100-140g/l, wherein the soaking temperature is 20-30 ℃, the soaking time is 30-50 minutes, and the hemicellulose concentration of the soaking solution is less than 20 g/l;

the alkali liquor dipping step: adding an auxiliary agent liquid, wherein the addition amount of the auxiliary agent liquid is 2-4% of the impregnation alkali liquor; the auxiliary agent liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;

the method is characterized in that: the preparation method of the silk fibroin solution comprises the following steps:

a. boiling: placing silk in a pot with a temperature of 85-90 deg.C, and boiling for 10-20 min; after boiling, clockwise stirring for 5-10min, due to high temperature, the spatial structure of the protein can be denatured, but the surface colloid of the silk is not damaged, only the structure of the silk is loosened, and the silk is drawn out;

b. cutting the extracted fibroin tows into pieces smaller than 10 mm;

c. and putting the silk protein tow fragments into a dissolving solution with the mass of 4-5 times of that of the silk protein, and stirring and dissolving for 3-5 min.

2. The use of silk fibroin solution as defined in claim 1 for the preparation of regenerated cellulose fiber, wherein: the dissolving solution consists of sodium hydroxide, vitamin C, an auxiliary agent and water; in the dissolving solution, the mass ratio of the sodium hydroxide, the vitamin c, the auxiliary agent and the water is 15-30:5-10:8-15: 100-150.

3. The use of silk fibroin solution in regenerated cellulose fiber preparation according to claim 2, wherein: the auxiliary agent comprises the following components: propanol, Roman chamomile hydrosol and seaweed gel; the auxiliary agent comprises the following components in parts by weight: 10-15 parts of propanol, 5-8 parts of Roman chamomile hydrosol and 1-3 parts of seaweed gel.

4. The use of silk fibroin solution as defined in claim 1 for the preparation of regenerated cellulose fiber, wherein: the fiber defects are less than or equal to 1.1mg/100g, the long fiber rate is less than or equal to 0.2 percent, the double-length fiber is less than or equal to 0.5mg/100mg, the length deviation rate is less than or equal to +/-2 percent, and the whiteness is more than or equal to 80 percent.

5. The use of silk fibroin solution as defined in claim 1 for the preparation of regenerated cellulose fiber, wherein: the cellulose activation step: the concentration of hydrogen peroxide in the slurry is 15-20 g/L; heating the slurry to 40-55 deg.C in the slurry pool, and stirring for 30-40 min.

6. The use of silk fibroin solution as defined in claim 1 for the preparation of regenerated cellulose fiber, wherein: the primary squeezing temperature is 25-30 ℃, and the squeezing multiple is 2-2.3 times.

7. The use of silk fibroin solution as defined in claim 1 for the preparation of regenerated cellulose fiber, wherein: the auxiliary agent liquid comprises the following components in parts by weight: 2-5 parts of OS-406, 0.8-1.5 parts of dibutyl hydroxy toluene, 3-6 parts of ethanol, 1-3 parts of sodium carbonate and 40-50 parts of deionized water.