CN111910281A - Environment-friendly flame-retardant viscose fiber and preparation method thereof - Google Patents
Environment-friendly flame-retardant viscose fiber and preparation method thereof Download PDFInfo
- Publication number
- CN111910281A CN111910281A CN202010589424.1A CN202010589424A CN111910281A CN 111910281 A CN111910281 A CN 111910281A CN 202010589424 A CN202010589424 A CN 202010589424A CN 111910281 A CN111910281 A CN 111910281A
- Authority
- CN
- China
- Prior art keywords
- environment
- friendly flame
- retardant
- viscose
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- 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
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
- D01D5/06—Wet spinning methods
-
- 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
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
Abstract
The invention discloses an environment-friendly flame-retardant viscose fiber and a preparation method thereof, belonging to the field of flame-retardant viscose fibers. The invention uniformly mixes the viscose spinning solution and the composite environment-friendly flame retardant to obtain environment-friendly flame-retardant viscose mixed solution, sprays the mixed solution through a spinneret plate, and solidifies in a coagulating bath to obtain the environment-friendly flame-retardant viscose fiber. The preparation method of the composite environment-friendly flame retardant comprises the following steps: uniformly grinding the nitrogenous ring cage-shaped phosphate, the sodium citrate dihydrate solution, the boric acid solution and the silane coupling agent in a ball mill to prepare the composite environment-friendly flame retardant. The composite environment-friendly flame retardant prepared by the invention has good stability and dispersibility, and can obtain environment-friendly flame-retardant viscose fiber with excellent flame retardance, high strength, high elongation at break, high wet modulus and good alkali resistance.
Description
Technical Field
The invention belongs to the field of flame-retardant viscose fibers, and particularly relates to an environment-friendly flame-retardant viscose fiber and a preparation method thereof.
Background
The viscose fiber has the excellent performances of good hygroscopicity, strong air permeability, good dyeability, comfortable wearing, easy textile processing, biodegradability and the like which are incomparable with synthetic fibers. And the resource of the basic raw material, namely cellulose, is unlimited, and the outstanding advantages are biodegradability and renewability. This is of great significance from the viewpoint of environmental protection, green chemistry and solving energy problems. However, the viscose regenerated cellulose fiber is easy to burn and poor in flame retardant property, the limited oxygen index is only 19, and the dry-wet strength and modulus are low, so that the application of the viscose regenerated cellulose fiber is seriously influenced. Since textile is often the initial fire-retardant material of fire, it is necessary to develop flame-retardant fabrics to eliminate the fire and ensure the safety of people's lives and properties.
With the development of chemical synthesis technology and scientific research methods, the varieties of flame retardants are increasing, and people have deeper and deeper understanding on the properties of the flame retardants. Non-halogenation, smoke suppression and attenuation of flame retardants have become the leading topic in the field of current and future flame retardant research, but new nitrogen-based flame retardants with excellent performance are continuously moving from the laboratory to the market. For example, in the prior art, an authorization publication number CN106884310B discloses a flame retardant viscose fiber and a preparation method thereof, wherein the preparation steps mainly comprise preparation, spinning and collection of viscose spinning solution. The inorganic metal flame retardant is microencapsulated by an in-situ polymerization method to prepare the spherical nano microcapsule flame retardant, the average diameter of a sphere is 80-120 nm, the surface of the sphere is polychloropropene, the preparation of the nano microcapsule flame retardant is not only beneficial to the uniform distribution of the inorganic metal flame retardant on the surface of viscose fiber and the reduction of the dosage of the flame retardant, but also beneficial to the improvement of the flame retardant effect of the viscose fiber, and the limit oxygen index of the nano microcapsule flame retardant reaches more than 31.3 percent. The publication No. CN104641025B discloses a halogen-containing flame-retardant fiber, a method for producing the same, and a flame-retardant fiber product using the same, wherein the halogen-containing flame-retardant fiber comprises a halogen-containing polymer and a molybdenum compound, wherein the average particle diameter of the molybdenum compound, expressed by the median diameter, is 10nm or more and less than 600nm, and a halogen-containing flame-retardant fiber highly flame-retarded by the halogen-containing fiber, a method for producing the same, and a flame-retardant fiber product using the same are obtained.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly flame-retardant viscose fiber of a stable composite environment-friendly flame retardant, which has low smoke, low toxicity, no halogen, excellent flame retardance, high strength, high elongation at break, high wet modulus and good alkali resistance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of environment-friendly flame-retardant viscose fibers comprises the following steps:
(1) preparing viscose spinning solution; impregnating, squeezing, crushing, aging, yellowing, dissolving, curing, defoaming and filtering wood fibers to prepare a viscose spinning solution;
(2) preparation of environment-friendly flame-retardant viscose raw yarn
Preparing a composite environment-friendly flame retardant: putting the nitrogenous ring cage-shaped phosphate, the sodium citrate dihydrate solution and the boric acid solution into a ball mill, and uniformly mixing under the stirring action; then slowly adding a silane coupling agent into a ball mill, and mixing uniformly to prepare the composite environment-friendly flame retardant;
uniformly mixing the obtained viscose spinning solution with the composite environment-friendly flame retardant to obtain an environment-friendly flame-retardant viscose mixed solution, spraying the environment-friendly flame-retardant viscose mixed solution output by a metering pump through a spinneret plate, and curing and forming through a coagulating bath to obtain environment-friendly flame-retardant viscose raw yarn;
(3) preparing environment-friendly flame-retardant viscose fibers: and washing, pickling and drying the environment-friendly flame-retardant viscose raw yarn to obtain the environment-friendly flame-retardant viscose fiber.
Preferably, in the step (1), the concentration of cellulose in the viscose fiber precursor is 25-29%.
Preferably, in the step (1), the viscosity of the viscose fiber spinning solution is 30-35 pas.
Preferably, step (2) is:
the preparation method of the composite environment-friendly flame retardant comprises the following steps of: uniformly grinding 6-10 parts of nitrogen-containing ring cage-shaped phosphate, 0.5-1 part of sodium citrate dihydrate solution, 2-5 parts of boric acid solution and 0.5-5 parts of silane coupling agent in a ball mill to prepare the composite environment-friendly flame retardant;
and uniformly mixing 85-95 parts of the obtained viscose spinning solution with the composite environment-friendly flame retardant to obtain an environment-friendly flame-retardant viscose mixed solution, spraying the environment-friendly flame-retardant viscose mixed solution output by the metering pump through a spinneret plate, and curing and molding through a coagulating bath to obtain the environment-friendly flame-retardant viscose precursor.
The invention adopts nitrogenous ring cage-shaped phosphate, sodium citrate dihydrate solution and boronAcid solution and silane coupling agent are used as environment-friendly fire retardant raw materials, sodium citrate dihydrate in the sodium citrate dihydrate solution generates more carboxyl after being diluted by water, and boron in the boric acid solution is mainly B (OH)4 -The sodium citrate dihydrate solution and the boric acid solution can be complexed to form a mixed solution with a stable structure; the hydrophilic group in the silane coupling agent is hydrolyzed to form silanol, so that one end of the silane coupling agent can be firmly combined with the mixed solution of the sodium citrate dihydrate solution and the boric acid solution; the nitrogenous ring cage-shaped phosphate ester contains a phosphorus ester bond which reacts with an organic functional group at the other end of the silane coupling agent, so that the phosphate ester bond and the organic functional group are stably combined to form the composite environment-friendly flame retardant with a firm structure; the composite environment-friendly flame retardant has excellent acid-base regulation performance and buffering performance, can form environment-friendly flame-retardant viscose mixed liquid with good stability and dispersibility by combining with viscose spinning solution, greatly improves the flame-retardant durability and flame-retardant efficiency of viscose fiber, and improves the spinnability of the environment-friendly flame-retardant viscose mixed liquid to a certain extent. In addition, on one hand, the composite environment-friendly flame retardant can form a carbonaceous layer on the surface of the viscose fiber to prevent the viscose fiber from further burning, simultaneously generate non-combustible gas and reduce the concentration of the combustible gas generated in the cellulose decomposition process; on the other hand, the physical and mechanical properties of the fiber are better improved, and the environment-friendly flame-retardant viscose fiber which is low in smoke, low in toxicity, free of halogen, excellent in flame retardance, high in strength, high in elongation at break, high in wet modulus and good in alkali resistance is obtained.
Preferably, in the step (2), the silane coupling agent in the environment-friendly composite flame retardant is one or a mixture of several of KH550, YDH550, KH590 and KH 792.
Preferably, in the step (2), the concentration of the sodium citrate dihydrate solution in the composite environment-friendly flame retardant is 1-5 wt%, and the concentration of the boric acid solution is 1-5 wt%.
Preferably, in the step (2), the concentration of the silane coupling agent solution in the composite environment-friendly flame retardant is 0.2-1.5%.
Preferably, in the step (2), the particle size of the composite environment-friendly flame retardant is 250-450 nm.
Preferably, in step (2), the coagulation bath has the following composition: 87-93 g/L of sulfuric acid, 10-12 g/L of zinc sulfate and 225-235 g/L of sodium sulfate; the temperature of the coagulating bath is 55-60 ℃.
Preferably, in the step (3), the drying temperature of the viscose raw silk is 65-70 ℃.
In order to further improve the strength, elongation at break and wet modulus of the environmentally friendly flame retardant viscose fiber, preferred measures further include:
adding a mixture of dimethyl 2-hydroxyethyl phosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane into a viscose fiber coagulation bath, wherein the addition amount of the mixture in the coagulation bath is 0.5-3 g/L, and the weight of the dimethyl 2-hydroxyethyl phosphonate, the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and the isobutyl germane is 0.5-1: 0.8-1.5: 0.2-0.4; 2-hydroxyethyl phosphonic acid dimethyl ester, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane are added into a coagulating bath and interact with sulfuric acid, zinc sulfate and sodium sulfate in the coagulating bath, so that the diffusion rate of components of a coagulating agent is better slowed down in the coagulating bath, the regeneration of fibers is delayed, the crystallinity and the orientation degree of a fiber skin layer are increased, and the strength and the elongation at break of the fibers are further improved; meanwhile, the water absorption of the viscose fiber is greatly increased, and the wet modulus of the environment-friendly flame-retardant viscose fiber is further improved.
Compared with the prior art, the environment-friendly flame-retardant viscose fiber is obtained by mixing the viscose spinning solution and the composite environment-friendly flame retardant to obtain environment-friendly flame-retardant viscose mixed solution, then spraying the environment-friendly flame-retardant viscose mixed solution through a spinneret plate, and curing the environment-friendly flame-retardant viscose mixed solution in a coagulating bath. Therefore, the following beneficial effects are achieved: according to the invention, the nitrogen-containing ring cage-shaped phosphate, the sodium citrate dihydrate solution, the boric acid solution and the silane coupling agent are adopted to prepare the environment-friendly flame retardant, and the environment-friendly flame retardant is mixed with the viscose spinning solution to form environment-friendly flame-retardant viscose mixed solution with good stability and dispersibility, so that the flame-retardant durability and the flame-retardant efficiency of the viscose fiber are greatly improved; the environment-friendly flame-retardant viscose fiber is low in smoke, low in toxicity, free of halogen, excellent in flame retardance, high in strength, high in elongation at break, high in wet modulus and good in alkali resistance. Therefore, the invention is a preparation method of the environment-friendly flame-retardant viscose fiber of the stable composite environment-friendly flame retardant, and the environment-friendly flame-retardant viscose fiber has low smoke, low toxicity, no halogen, excellent flame retardance, high strength, high elongation at break, high wet modulus and good alkali resistance.
Drawings
FIG. 1 is a diagram showing the limiting oxygen index of an environmentally friendly flame retardant viscose fiber;
FIG. 2 shows the breaking strength of the environmentally friendly flame retardant viscose fiber;
FIG. 3 shows the elongation at break of the environmentally friendly flame retardant viscose fiber;
FIG. 4 shows the strength loss and elongation loss of the environmentally friendly flame retardant viscose fiber;
FIG. 5 shows the wet modulus of the eco-friendly flame retardant viscose fiber.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1
A preparation method of environment-friendly flame-retardant viscose fibers comprises the following steps:
(1) preparation of viscose spinning solution
The viscose spinning solution is prepared by impregnating, squeezing, crushing, aging, yellowing, dissolving, curing, defoaming and filtering wood fibers by adopting a conventional preparation process, the cellulose concentration of viscose is 25%, and the viscosity of the viscose spinning solution is 32 Pa.s.
(2) Preparation of environment-friendly flame-retardant viscose raw yarn
Putting 6 parts of nitrogenous ring cage-shaped phosphate, 0.8 part of sodium citrate dihydrate solution with the concentration of 6 wt% and 3 parts of boric acid solution with the concentration of 4 wt% in parts by weight into a ball mill, and uniformly mixing under the stirring action at the stirring speed of 115 r/min; then slowly adding 2 parts of YDH550 with the concentration of 0.5 percent, and mixing uniformly to prepare the composite environment-friendly flame retardant.
Mixing 87 parts of the viscose spinning solution obtained in the step (1) and the obtained composite environment-friendly flame retardant uniformly under the stirring action, wherein the stirring speed is 350r/min, the stirring time is 0.5-1 h, the particle size of the composite environment-friendly flame retardant is 280-300 nm measured by an LS13320XR laser diffraction particle size analyzer, so as to obtain an environment-friendly flame-retardant viscose mixed solution, spraying the environment-friendly flame-retardant viscose mixed solution output by a metering pump through a spinneret plate with the aperture of 0.07mm, and then curing and molding through a coagulating bath, so as to obtain environment-friendly flame-retardant viscose precursor; the coagulation bath consisted of: 89g/L of sulfuric acid, 10g/L of zinc sulfate and 225g/L of sodium sulfate; the coagulation bath temperature was 56 ℃.
(3) Preparation of environment-friendly flame-retardant viscose fiber
And (3) washing and acid-washing the environment-friendly flame-retardant viscose raw yarn obtained in the step (2), and drying at 65 ℃ to obtain the environment-friendly flame-retardant viscose fiber.
Example 2
A preparation method of environment-friendly flame-retardant viscose fibers comprises the following steps:
(1) preparation of viscose spinning solution
The viscose spinning solution is prepared by impregnating, squeezing, crushing, aging, yellowing, dissolving, curing, defoaming and filtering wood fibers by adopting a conventional preparation process, wherein the cellulose concentration of viscose is 28 percent, and the viscosity of the viscose spinning solution is 34 pas.
(2) Preparation of environment-friendly flame-retardant viscose raw yarn
Putting 7 parts by weight of nitrogenous ring cage-shaped phosphate, 0.6 part by weight of 9 wt% sodium citrate dihydrate solution and 2 parts by weight of 3 wt% boric acid solution into a ball mill, and uniformly mixing under the stirring action at the stirring speed of 120 r/min; then slowly adding 3 parts of KH590 with the concentration of 0.7 percent until the mixture is uniformly mixed, and preparing the composite environment-friendly flame retardant.
Mixing 85 parts of the viscose spinning solution obtained in the step (1) and the obtained composite environment-friendly flame retardant uniformly under the stirring action, wherein the stirring speed is 400r/min, the stirring time is 0.5-1 h, the particle size of the composite environment-friendly flame retardant is measured to be 295-320 nm, an environment-friendly flame retardant viscose mixed solution is obtained, and then the environment-friendly flame retardant viscose mixed solution output by a metering pump is sprayed out through a spinneret plate with the aperture of 0.09mm and is solidified and molded through a coagulating bath, so that environment-friendly flame retardant viscose precursor fibers are obtained; the coagulation bath consisted of: 90g/L of sulfuric acid, 11g/L of zinc sulfate and 227g/L of sodium sulfate; the temperature of the coagulation bath was 60 ℃.
(3) Preparation of environment-friendly flame-retardant viscose fiber
And (3) washing and acid-washing the environment-friendly flame-retardant viscose raw fiber obtained in the step (2), and drying at 68 ℃ to obtain the environment-friendly flame-retardant viscose fiber.
Example 3
A preparation method of environment-friendly flame-retardant viscose fibers comprises the following steps:
(1) preparation of viscose spinning solution
The viscose spinning solution is prepared by impregnating, squeezing, crushing, aging, yellowing, dissolving, curing, defoaming and filtering wood fibers by adopting a conventional preparation process, the cellulose concentration of viscose is 27%, and the viscosity of the viscose spinning solution is 31 Pa.s.
(2) Preparation of environment-friendly flame-retardant viscose raw yarn
According to parts by weight, 9 parts of nitrogenous ring cage-shaped phosphate, 1 part of sodium citrate dihydrate solution with the concentration of 7 wt% and 2 parts of boric acid solution with the concentration of 1.5 wt% are placed in a ball mill and are uniformly mixed under the stirring action, and the stirring speed is 120 r/min; then slowly adding 3 parts of KH590 with the concentration of 0.9 percent until the mixture is uniformly mixed, and preparing the composite environment-friendly flame retardant.
Uniformly mixing 90 parts of the viscose spinning solution obtained in the step (1) with the obtained composite environment-friendly flame retardant under the stirring action, wherein the stirring speed is 450r/min, the stirring time is 0.5-1 h, the particle size of the composite environment-friendly flame retardant is measured to be 350-400 nm, an environment-friendly flame retardant viscose mixed solution is obtained, and then the environment-friendly flame retardant viscose mixed solution output by a metering pump is sprayed out through a spinneret plate with the aperture of 0.09mm and is solidified and molded through a coagulating bath, so that environment-friendly flame retardant viscose precursor fibers are obtained; the coagulation bath consisted of: 91g/L sulfuric acid, 12g/L zinc sulfate and 231g/L sodium sulfate; the temperature of the coagulation bath was 60 ℃.
(3) Preparation of environment-friendly flame-retardant viscose fiber
And (3) washing and acid-washing the environment-friendly flame-retardant viscose raw yarn obtained in the step (2), and drying at 70 ℃ to obtain the environment-friendly flame-retardant viscose fiber.
Example 4
Different from the embodiment 2, the preparation method of the environment-friendly flame-retardant viscose fiber is characterized in that a sodium citrate dihydrate solution is not added in the process of preparing the composite environment-friendly flame retardant in the step (2).
Example 5
Different from the embodiment 2, the preparation method of the environment-friendly flame-retardant viscose fiber is characterized in that a boric acid solution is not added in the process of preparing the composite environment-friendly flame retardant in the step (2).
Example 6
Different from the embodiment 2, the preparation method of the environment-friendly flame-retardant viscose fiber does not add sodium citrate dihydrate and boric acid solution in the process of preparing the composite environment-friendly flame retardant in the step (2).
Example 7
Different from the embodiment 2, in the step (2), the composition of the coagulating bath is as follows: 90g/L sulfuric acid, 11g/L zinc sulfate, 227g/L sodium sulfate, 0.7 g/L2-a mixture of dimethyl hydroxyethyl phosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane, wherein the weight percentage of the dimethyl 2-hydroxyethyl phosphonate, the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and the isobutyl germane is 0.6:1: 0.3; the temperature of the coagulation bath was 60 ℃.
Example 8
Different from the embodiment 7, the preparation method of the environment-friendly flame-retardant viscose fiber comprises the following steps of (2) and the coagulation bath: 90g/L sulfuric acid, 11g/L zinc sulfate, 227g/L sodium sulfate, 1.4 g/L2-a mixture of dimethyl hydroxyethyl phosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane, wherein the weight percentage of the dimethyl 2-hydroxyethyl phosphonate, the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and the isobutyl germane is 0.7:1.1: 0.2; the temperature of the coagulation bath was 60 ℃.
Example 9
Different from the embodiment 7, the preparation method of the environment-friendly flame-retardant viscose fiber comprises the following steps of (2) and the coagulation bath: 90g/L sulfuric acid, 11g/L zinc sulfate, 227g/L sodium sulfate, 2.0 g/L2-a mixture of dimethyl hydroxyethyl phosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane, wherein the weight percentage of the dimethyl 2-hydroxyethyl phosphonate, the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and the isobutyl germane is 0.5:0.9: 0.4; the temperature of the coagulation bath was 60 ℃.
Example 10
Different from the embodiment 7, in the step (2), dimethyl 2-hydroxyethyl phosphonate is not added into the components of the coagulating bath.
Example 11
Unlike example 7, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate is not added to the coagulation bath component in step (2).
Example 12
Different from the embodiment 7, in the step (2), isobutyl germane is not added into the components of the coagulating bath.
Example 13
Different from the embodiment 7, in the step (2), dimethyl 2-hydroxyethyl phosphonate and isobutyl germane are not added into the components of the coagulating bath.
Example 14
Unlike example 7, in step (2), dimethyl 2-hydroxyethyl phosphonate and octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are not added to the coagulation bath components.
Example 15
Different from the embodiment 7, in the step (2), octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane are not added into the coagulating bath components.
Test example 1
1. Determination of environment-friendly flame-retardant viscose mixed liquid stability
The obtained environment-friendly flame-retardant viscose mixed solution is defoamed in a centrifuge at the speed of 5000rad/m for 3min, and then the steady-state rheological property of the mixture is measured. All rheological measurements were carried outPerforming stress control rheometer (ARES-RFS of TA of America) at 0, 5, 10, and 20 deg.C, controlling temperature error at + -0.3 deg.C under the action of condensed liquid (glycerol: water: 1), and shearing rate at 0.2-400 s-1. And preparing a cellulose solution with the cellulose solid content of 6.2 wt%, mixing the cellulose solution with the flame retardant, and performing a steady-state rheological test. The structural viscosity index is an important index for representing the solution rheology, can represent the structuring degree of the spinning solution, and when the spinning performance is ensured, the reduction of the structural viscosity index of the cellulose, namely the reduction of the structuring degree of the solution, is helpful for improving the spinnability of the solution. Which can be calculated from steady state rheological experimental tests of the solution. The equation for calculating the structural viscosity index is as follows:
wherein the content of the first and second substances,
Δ μ — structural viscosity index;
μ -shear viscosity;
gamma-shear rate.
The environmental-friendly flame-retardant viscose mixed liquor of the embodiments 1 to 6 is subjected to a steady-state rheological test, and the structural viscosity index is shown in table 1:
TABLE 1 structural viscosity index
Table 1 shows the structural viscosity index of the environmentally friendly flame retardant adhesive mixture. As can be seen from table 1, the structural viscosity indexes of examples 1 to 3 are all lower than 1.5, the spinnability of the flame retardant is superior to that of examples 4 to 6, and the structural viscosity indexes of examples 4 to 5 are lower than that of example 6, which indicates that sodium citrate dihydrate and boric acid solution are simultaneously added to the flame retardant, so that the flame retardant can be combined with nitrogen-containing ring cage-shaped phosphate and silane coupling agent to form a composite environment-friendly flame retardant with a firm structure, the flame retardant has excellent acid-base regulation performance and buffering performance, and can be combined with viscose spinning solution to form environment-friendly flame retardant viscose mixed liquid with good stability and dispersibility, and the spinnability of the environment-friendly flame retardant viscose mixed liquid is improved to a certain extent.
2. Determination of limit oxygen index of environment-friendly flame-retardant viscose fiber
Flame retardant property: according to the standard of ASTMD2863-70, the fiber is woven into 262g/m by using a conventional one-type oxygen index instrument2After the yarn was seized, the sample was cut into a standard sample and measured.
Fig. 1 is a limit oxygen index of the environment-friendly flame-retardant viscose fiber. As can be seen from fig. 1, the limiting oxygen indexes of examples 1 to 3 are all higher than 35, and the limiting oxygen indexes of examples 1 to 3 are much higher than those of examples 4 to 6, and examples 4 to 5 are much higher than those of example 6, which shows that the flame retardancy of the viscose fiber is improved by adding sodium citrate dihydrate and boric acid solution into the flame retardant at the same time, probably because the sodium citrate dihydrate and boric acid solution are combined with nitrogen-containing ring cage-shaped phosphate and silane coupling agent to form a composite environment-friendly flame retardant with a firm structure, the composite environment-friendly flame retardant contains hydroxyl and coupling agent, and has excellent acid-base adjusting performance and buffering performance, and then is combined with the viscose spinning solution to form an environment-friendly flame retardant viscose mixed solution with good stability and dispersibility, so as to greatly improve the flame retardancy durability and flame retardant efficiency of the viscose fiber, in addition, this compound environment-friendly flame retardant can form the carbonaceous layer on the viscose fiber surface on the one hand, prevents viscose fiber further burning, produces incombustible gas simultaneously, reduces the concentration of the combustible gas that produces in the cellulose decomposition process. The limiting oxygen indexes of the embodiments 7-9 are all higher than 36, the limiting oxygen indexes of the embodiments 7-9 and the embodiments 2 are higher than that of the embodiment 2, the limiting oxygen indexes of the embodiments 7-9 and the embodiments 10-15 are higher than that of the embodiments 10-15, and the limiting oxygen indexes of the embodiments 1-3 are higher than that of the embodiments 10-15, which shows that the flame retardance of the viscose fiber can be further improved by adding the mixture of the dimethyl 2-hydroxyethyl phosphonate, the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane, and only one or two of the mixtures have a certain negative influence on the flame retardance of the environment-friendly flame retardant viscose fiber.
3. Environment-friendly flame-retardant viscose fiber monofilament strength test
The mechanical properties of the fibers are tested by adopting an XQ-1 type single fiber electronic strength tester. The pretension is 0.1cN, the effective fiber holding length is 10mm, and the drawing speed is 10 mm/min. The average of the 20 measurements is taken and the CV% value is close to or equal to 10%, which gives the strength and elongation at break of the fiber.
FIG. 2 shows the breaking strength of the environmentally friendly flame retardant viscose fiber. As can be seen from FIG. 2, the breaking strength of examples 1-3 is higher than 2.5cN/dtex, the breaking strength of example 2 is higher than 3cN/dtex, compare examples 1-3 with examples 4-6, the breaking strength of examples 1-3 is higher than examples 4-6, which shows that sodium citrate dihydrate and boric acid solution are added into the flame retardant at the same time, both of which can be combined with nitrogen-containing ring cage phosphate and silane coupling agent to form a composite environment-friendly flame retardant with a firm structure, and then combined with the viscose spinning solution to form an environment-friendly flame retardant viscose mixed solution with good stability and dispersibility, thereby improving the breaking strength of viscose fibers. Examples 7-9 all had a breaking strength of greater than 3.6cN/dtex, comparative examples 7-9 and example 2, examples 7-9 had a breaking strength greater than example 2, comparing examples 7-9 with examples 10-15, examples 7-9 all had higher breaking strengths than examples 10-15, and the fracture strength of the embodiments 1-3 is higher than that of the embodiments 10-15, which shows that the simultaneous addition of the mixture of dimethyl 2-hydroxyethyl phosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane in the coagulating bath better slows down the diffusion rate of the components of the coagulating agent, delays the regeneration of the fiber, increases the crystallinity and orientation degree of the fiber skin layer, further improves the fiber strength, and only one or two of the mixtures can influence the fracture strength of the fiber to a certain extent.
FIG. 3 shows the elongation at break of the environmentally friendly flame retardant viscose fiber. As can be seen from fig. 3, the elongation at break of examples 1 to 3 is higher than 19.5%, the elongation at break of comparative examples 1 to 3 and examples 4 to 6, and the elongation at break of examples 1 to 3 is higher than that of examples 4 to 6, which means that sodium citrate dihydrate and boric acid solution are added to the flame retardant at the same time, and both of them may be combined with nitrogen-containing ring cage phosphate and silane coupling agent to form a composite environment-friendly flame retardant with a firm structure, and then combined with the viscose spinning solution, an environment-friendly flame retardant viscose mixed solution with good stability and dispersibility can be formed, and the elongation at break of the viscose fiber is improved. The elongation at break of the fibers is higher than 22% in examples 7-9, higher than that of example 2 in comparative examples 7-9 and 2 in examples 7-9, higher than that of examples 10-15 in comparative examples 7-9 and 10-15 in examples 7-9, and higher than that of examples 10-15 in examples 1-3, which shows that the elongation at break of the fibers is further improved by adding the mixture of dimethyl 2-hydroxyethylphosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane, and that the elongation at break of the fibers is reduced to some extent by adding only one or two of the mixtures.
4. Determination of alkali resistance of environment-friendly flame-retardant viscose
Appropriate amount of fiber is extracted from the sample, and the fiber is soaked in 0.75mol/l of sodium hydroxide solution prepared in advance for 8min, and then is washed with water for many times, and is detected by pH paper test paper until the pH value is close to neutral. And (3) placing the treated fiber at normal temperature for airing for more than 72 hours. The mechanical property of the fiber is measured by adopting an XQ-1 type single fiber electronic strength tester, the fiber number is tested for more than 20 times, and the CV percent value is close to or equal to 10 percent. The fibers without any treatment were taken as a control group, and the loss rate of strength and elongation at break was calculated by the following formula:
strength loss rate (treated fiber strength-untreated fiber strength) ÷ untreated fiber strength × 100%
Elongation at break loss ═ (treated fiber elongation-untreated fiber elongation) ÷ untreated fiber elongation × 100%
FIG. 4 shows the strength loss rate and elongation at break loss rate of the environmentally friendly flame retardant viscose fiber. As can be seen from fig. 4, the strength loss rate of examples 1 to 3 is less than 13%, the strength loss rate of comparative examples 1 to 3 and examples 4 to 6, and the strength loss rate of examples 1 to 3 is less than examples 4 to 6, which indicates that sodium citrate dihydrate and boric acid solution are added to the flame retardant simultaneously, and both of them may be combined with nitrogen-containing ring cage phosphate and silane coupling agent to form a composite environment-friendly flame retardant with a firm structure, and then combined with the viscose spinning solution to form an environment-friendly flame retardant viscose mixed solution with good stability and dispersibility, which can improve the alkali resistance of the viscose fiber. The strength loss rate of the fibers of examples 7-9 is lower than 9%, the strength loss rate of the fibers of comparative examples 7-9 and 2 is lower than that of example 2, the strength loss rate of the fibers of comparative examples 7-9 and 10-15 is lower than that of examples 7-9, and the strength loss rate of the fibers of examples 1-3 is lower than that of examples 10-15, which shows that the strength and alkali resistance of the fibers are further improved by adding the mixture of dimethyl 2-hydroxyethylphosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane at the same time, and only one or two of the mixtures can influence the alkali resistance of the fibers to a certain extent.
As can be seen from fig. 4, the elongation at break loss of examples 1 to 3 is less than 15%, the elongation at break loss of comparative examples 1 to 3 and examples 4 to 6, and the elongation at break loss of examples 1 to 3 is less than that of examples 4 to 6, which means that sodium citrate dihydrate and boric acid solution are added to the flame retardant at the same time, and both of them may be combined with the nitrogen-containing ring cage phosphate and the silane coupling agent to form a composite environment-friendly flame retardant with a firm structure, and then combined with the viscose spinning solution to form an environment-friendly flame retardant viscose mixed solution with good stability and dispersibility, which can improve the alkali resistance of the viscose fibers. The elongation at break loss of examples 7-9 is less than 13%, the elongation at break loss of examples 7-9 and examples 2, the elongation at break loss of examples 7-9 is less than that of example 2, the elongation at break loss of examples 7-9 and examples 10-15 is less than that of examples 10-15, and the elongation at break loss of examples 1-3 is less than that of examples 10-15, which shows that the simultaneous addition of the mixture of dimethyl 2-hydroxyethylphosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane further improves the alkali resistance of the fibers, and the addition of only one or two of the mixtures has a negative effect on the alkali resistance of the viscose fibers.
5. Determination of wet modulus of environment-friendly flame-retardant viscose
The modulus of a fiber in the wet state is usually expressed as the load required to elongate the wet fiber by 5% multiplied by 20. The Young's modulus E value of a fiber can be obtained from an initial linear portion fit of the monofilament stress-strain curve when directly measuring the fiber strain according to ASTM1557-03(2008) standard. This experiment measures the wet environment-friendly flame-retardant viscose fiber 20 times, and takes the average value.
FIG. 5 shows the wet modulus of the eco-friendly flame retardant viscose fiber. As can be seen from FIG. 5, the wet modulus of examples 1-3 is greater than 88cN/tex, and the wet modulus of comparative examples 1-3 and examples 4-6 is higher than that of examples 1-3, which shows that the wet modulus of the eco-friendly flame retardant viscose fiber can be further improved by adding sodium citrate dihydrate and boric acid solution to the flame retardant. The wet modulus of the examples 7-9 is higher than 98cN/tex, the wet modulus of the comparative examples 7-9 and 2, the wet modulus of the examples 7-9 is higher than that of the example 2, the wet modulus of the comparative examples 7-9 and 10-15, the wet modulus of the examples 7-9 is higher than that of the examples 10-15, and the wet modulus of the examples 1-3 is higher than that of the examples 10-15, which shows that the simultaneous addition of the mixture of dimethyl 2-hydroxyethyl phosphonate, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and isobutyl germane greatly increases the water absorption of the viscose fiber, and further increases the wet modulus of the environment-friendly flame retardant viscose fiber, and the addition of only one or two of the mixtures reduces the wet modulus of the fiber to a certain extent.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A preparation method of environment-friendly flame-retardant viscose fibers comprises the following steps:
(1) preparing viscose spinning solution; impregnating, squeezing, crushing, aging, yellowing, dissolving, curing, defoaming and filtering wood fibers to prepare a viscose spinning solution;
(2) preparing environment-friendly flame-retardant viscose raw yarns:
preparing a composite environment-friendly flame retardant: putting the nitrogenous ring cage-shaped phosphate, the sodium citrate dihydrate solution and the boric acid solution into a ball mill, and uniformly mixing under the stirring action; then slowly adding a silane coupling agent into a ball mill, and mixing uniformly to prepare the composite environment-friendly flame retardant;
and uniformly mixing the obtained viscose spinning solution with the composite environment-friendly flame retardant to obtain an environment-friendly flame-retardant viscose mixed solution, spraying the environment-friendly flame-retardant viscose mixed solution output by the metering pump through a spinneret plate, and solidifying and forming through a coagulating bath to obtain the environment-friendly flame-retardant viscose raw yarn.
(3) Preparing environment-friendly flame-retardant viscose fibers: and washing, pickling and drying the environment-friendly flame-retardant viscose raw yarn to obtain the environment-friendly flame-retardant viscose fiber.
2. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (1), the cellulose concentration in the viscose fiber precursor is 25-29%.
3. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (1), the viscosity of the viscose spinning solution is 30-35 Pa.s.
4. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (2), the silane coupling agent in the composite environment-friendly flame retardant is one or a mixture of several of KH550, YDH550, KH590 and KH 792.
5. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (2), the concentration of the sodium citrate dihydrate solution in the composite environment-friendly flame retardant is 5-10 wt%, and the concentration of the boric acid solution is 1-5 wt%.
6. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (2), the concentration of the silane coupling agent solution in the composite environment-friendly flame retardant is 0.2-1.5%.
7. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (2), the particle size of the composite environment-friendly flame retardant is 250-450 nm.
8. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (2), the coagulation bath comprises the following components: 87-93 g/L of sulfuric acid, 10-12 g/L of zinc sulfate and 225-235 g/L of sodium sulfate; the temperature of the coagulating bath is 55-60 ℃.
9. The preparation method of the environment-friendly flame-retardant viscose fiber according to claim 1, which is characterized by comprising the following steps: in the step (3), the drying temperature of the viscose raw silk is 65-70 ℃.
10. The environment-friendly flame-retardant viscose fiber prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010589424.1A CN111910281A (en) | 2020-06-24 | 2020-06-24 | Environment-friendly flame-retardant viscose fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010589424.1A CN111910281A (en) | 2020-06-24 | 2020-06-24 | Environment-friendly flame-retardant viscose fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111910281A true CN111910281A (en) | 2020-11-10 |
Family
ID=73226637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010589424.1A Withdrawn CN111910281A (en) | 2020-06-24 | 2020-06-24 | Environment-friendly flame-retardant viscose fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111910281A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112575582A (en) * | 2020-12-25 | 2021-03-30 | 福建七匹狼实业股份有限公司 | Stiff and smooth skin-friendly pure cotton fabric |
| CN115161036A (en) * | 2022-06-28 | 2022-10-11 | 苏州世名科技股份有限公司 | Environment-friendly flame retardant, preparation method and environment-friendly flame-retardant viscose fiber |
-
2020
- 2020-06-24 CN CN202010589424.1A patent/CN111910281A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112575582A (en) * | 2020-12-25 | 2021-03-30 | 福建七匹狼实业股份有限公司 | Stiff and smooth skin-friendly pure cotton fabric |
| CN115161036A (en) * | 2022-06-28 | 2022-10-11 | 苏州世名科技股份有限公司 | Environment-friendly flame retardant, preparation method and environment-friendly flame-retardant viscose fiber |
| CN115161036B (en) * | 2022-06-28 | 2024-02-02 | 苏州世名科技股份有限公司 | Environment-friendly flame retardant, preparation method and environment-friendly flame retardant viscose fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5417752A (en) | Product containing silicon dioxide and a method for its preparation | |
| AT502743B1 (en) | CELLULOSIC FORM BODY, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF | |
| CN102352539B (en) | Manufacturing method of silicon-nitrogen containing environmental protection and flame retardant viscose staple fiber | |
| CN105745368B (en) | Polysaccharide fiber and preparation method thereof | |
| WO2007121609A1 (en) | The use of aqueous solution of sodium-hydroxide and sulfourea in producing cellulose products in pilot-scale | |
| CN111910281A (en) | Environment-friendly flame-retardant viscose fiber and preparation method thereof | |
| CN109267318B (en) | Flame-retardant lyocell fiber and preparation method thereof | |
| CN101343781A (en) | Method of preparing flame-proof polyvinyl alcohol/SiO2 composite fiber | |
| CN114438771A (en) | Preparation method of biological hyaluronic acid flame-retardant polyester cotton based on complexation of reactive sericin and metal ions | |
| CN114437366B (en) | Intumescent flame retardant, preparation method and application thereof, flame-retardant polyacrylonitrile fiber and preparation method thereof | |
| CN114214750A (en) | Flame-retardant polyacrylonitrile composite fiber and preparation method and application thereof | |
| CN110184666A (en) | Spinning head used in the manufacturing method and manufacturing process of flame retardant cellulose fiber | |
| CN101089258A (en) | Method for preparing high strength cellulose and silicat composite fibre and prepared composite fibre | |
| CN113882029B (en) | High-strength water-resistant phosphorus-nitrogen flame-retardant viscose fiber and preparation method thereof | |
| Li et al. | Study on the structure and properties of viscose/wool powder blended fibre | |
| CN109440474B (en) | Low-specific-gravity flame-retardant viscose fiber and manufacturing method thereof | |
| CN109162096B (en) | Method for preparing flame-retardant Lyocell cellulose fiber based on post-treatment method | |
| CN113308889A (en) | Halogen-free flame-retardant polyester-cotton fabric and preparation method thereof | |
| CN116926705A (en) | Multifunctional regenerated cellulose fiber and preparation method thereof | |
| JP3345110B2 (en) | Multifilament or staple fiber composed of water-soluble polyvinyl alcohol fiber | |
| CN113862807B (en) | Flame-retardant lyocell filament and preparation method thereof | |
| CN112323159B (en) | Flame-retardant lyocell fiber and preparation method thereof | |
| CN110938885B (en) | Flame-retardant regenerated cellulose fiber and preparation method thereof | |
| CN113981693A (en) | Modified PP polypropylene resin for melt-blown material and preparation process thereof | |
| CN116411363A (en) | Preparation method of flame-retardant regenerated cellulose fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201110 |