CN107475794B - Silicon-nitrogen flame-retardant high-wet-modulus viscose fiber and preparation method thereof - Google Patents
Silicon-nitrogen flame-retardant high-wet-modulus viscose fiber and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The invention provides a silicon nitrogen flame-retardant high-wet-modulus viscose fiber, wherein the dry breaking strength of the fiber is more than or equal to 2.6CN/dtex, the wet breaking strength is more than or equal to 1.5CN/dtex, the limiting oxygen index is more than or equal to 30 percent, and the wet breaking modulus is more than or equal to 0.35 CN/dtex. The invention also provides a preparation method of the silicon nitrogen flame-retardant high wet modulus viscose fiber, which comprises the following steps: preparing cellulose sulfonate; preparing a spinning solution; a second injection step before spinning; the cellulose sulfonate preparation step comprises: carrying out yellowing reaction on cotton and/or wood pulp with the polymerization degree of 800-1400 to generate cellulose xanthate; the spinning solution preparation step comprises: dissolving cellulose xanthate in an alkali solution, adding a denaturant to obtain a spinning stock solution, and then preparing a spinning solution; the high-wet-modulus flame-retardant viscose fiber prepared by the invention has the characteristics of physical and mechanical properties and high wet modulus, and can be applied to the fields of high-grade textile garment materials with flame-retardant requirements and the like.
Description
Technical Field
The invention relates to a high wet modulus viscose fiber and a preparation method thereof, in particular to a silicon nitrogen series flame-retardant high wet modulus viscose fiber and a preparation method thereof, belonging to the field of production and preparation of textile raw materials.
Background
With the rapid development of the reform in nearly more than forty years, the consumption level of the Chinese people is steadily improved, and the demand of the fiber and the product thereof is increased day by day. However, while people consume a large amount of fiber products and enjoy the warmth, comfort and beauty of people, the fire caused by the combustion of the fiber products also becomes one of the major disasters of the modern society. The results of investigating the death accidents caused by fire show that the fire caused by indoor ornaments and textiles is the first, and meanwhile, the harmful gas released when the flammable textiles are combusted is far more harmful to human bodies than the flame-retardant textiles. Therefore, the development and production of high-quality flame-retardant fibers for preventing fire and reducing fire loss have been receiving increasing attention.
In foreign countries, the federal safety commission of the united states has made a 1633 act that is more stringent in requirements based on the original california TB603 standard in the united states against the enormous threat to the life safety of people from the continuous fire in the united states, and has been enforced in 50 states of the united states beginning at 7/1 of 2007, which act is primarily directed to the flame retardant properties of mattress products.
Under the background, companies such as FR of oridilin, composite flame-retardant fiber of finnish sardeli, VISIL, japan dahliang, hentianhailong, gilin chemical fiber, and beijing seolan continuously provide their flame-retardant viscose fiber products to meet social needs. The FR fiber of the semi-finished product has good performance and high price, and is difficult to enter common families. The silicon-based flame-retardant fibers of Japan Dahe, Hengtian Syngnathus have low strength, crisp and astringent hand feeling and high defects, and can only be used for manufacturing non-woven fabrics, mattresses and the like, but cannot be used in places such as spinning, weaving and the like. The phosphorus flame-retardant fibers, textiles and fire of the Jilin chemical fibers can generate a large amount of high-toxicity smoke, and fiber wastes can pollute water and the environment.
Patent CN102352539B introduces a new method for preparing silicon nitrogen flame-retardant fiber by adding flame retardant in the post-dissolution stage, which has the advantages of moderate price, environmental protection, no toxicity and better relative index, and well solves the defects and shortcomings. Patent CN106012074A optimizes the improvement on above-mentioned patent basis, adopt twice to spin the preceding injection technique and add fire-retardant auxiliary agent and fire retardant respectively, thereby very big reduction the loss rate and the spinning rate of trading the head of fire retardant, improved spinnability, improved flame retardant efficiency, do benefit to the continuous and stable production, but the information of market feedback sees, in the low reaches customer use, the spinning quality is not stable, the spinning burr produces more, weaving equipment's loss is great.
The biggest technical obstacle of continuous optimization and improvement of flame-retardant viscose fiber products is the contradiction between the improvement of the flame-retardant performance of the products and the improvement of the physical and mechanical properties of the fibers, and only the content of the flame retardant in the fibers is increased in order to improve the flame-retardant effect of the products, so that the physical and mechanical properties of the products are reduced. It is an inexhaustible idea of the above two patents that the silicon nitrogen flame-retardant fibers produced by the two technologies have excellent flame-retardant effect, but the strength is still slightly low, and the fibers are not satisfactory for subsequent links such as spinning and weaving. The wet modulus of the fiber is poor, the deformation of the fabric after washing is large, and the development of the fabric towards high-count yarn and high-grade fabrics with high technical content and high added value is greatly hindered.
Disclosure of Invention
The invention provides a method for producing silicon nitrogen flame-retardant viscose fiber, which comprises the steps of blending and adding a denaturant into a spinning solution prepared from pulp with higher polymerization degree, then adding a flame-retardant auxiliary agent and a flame retardant into the spinning solution by adopting a step-by-step pre-spinning injection technology, mixing and pre-reacting the flame-retardant auxiliary agent and viscose in advance to improve the combination activity and stability of the viscose and the flame retardant, then carrying out graft polymerization reaction on the viscose and the flame retardant, adopting a low-acid, low-sodium and high-zinc coagulation bath ratio and a high-magnification stepped drafting spinning process during spinning molding, and carrying out cross-linking curing treatment during post-treatment so as to finish the preparation of the high-wet-modulus silicon nitrogen flame-retardant fiber. The process not only solves the problems of slow combination of the flame retardant and the fiber and poor stability after combination, but also improves the physical and mechanical properties of the flame retardant fiber and endows the flame retardant fiber with the characteristic of high wet modulus.
The invention aims at the application defects of the existing silicon nitrogen flame-retardant fiber that the dry-wet strength and the wet modulus are relatively low, and provides a high-wet-modulus flame-retardant fiber and a preparation method of the high-wet-modulus flame-retardant fiber.
The preparation method of the high wet modulus flame-retardant fiber comprises the following steps:
a. preparation of cellulose sulfonate: fully mixing cotton and/or wood pulp with the polymerization degree of 800-1400 and the alpha cellulose content of more than or equal to 95% with an impregnation alkali liquor, and preparing alkali cellulose after impregnation and alkalization; the alkali cellulose is squeezed, crushed and aged, and then is mixed with CS2Mixing and carrying out yellowing reaction to generate cellulose xanthate;
b. preparing a spinning solution: dissolving cellulose xanthate in a dilute alkali solution, adding a denaturant with the concentration of 2.5-4.5% of alpha fibers into a post-dissolved alkali solution to obtain a spinning stock solution, and sequentially performing post-dissolving, three-pass filtering, defoaming and ripening on the spinning stock solution to obtain a spinning solution;
c. two pre-spinning injections: controlling the temperature of the spinning solution at 15-35 ℃ through a heat exchanger, injecting a flame retardant auxiliary agent with the flame retardant amount of 20-50wt% into the spinning solution through a one-pass pre-spinning injection system, mixing and pre-reacting through a static mixer, injecting a flame retardant with the methyl fiber amount of 20-50wt% into the spinning solution through a two-pass pre-spinning injection system, mixing through a dynamic mixer and a static mixer, entering a viscose mixer, carrying out graft polymerization reaction for 10-180 min in the mixer, and then spinning;
d. spinning: carrying out wet spinning in a spinning machine, extruding the spinning stock solution added with the flame retardant and the auxiliary agent by a nozzle, reacting with a spinning bath, and obtaining a nascent fiber tow by adopting a slow forming process;
e. drawing and post-treatment: the nascent fiber tows are subjected to three-level gradient drafting and plasticizing shaping by a spray head, a spinning disc and a plasticizing bath, and then are subjected to cutting and post-treatment, wherein the post-treatment process comprises pickling, crosslinking and curing, washing and oiling; and drying to obtain the high wet modulus flame-retardant fiber.
And further, the ageing temperature in the step a is 20-30 ℃, the ageing time is 1-4 hours, and the viscosity of the aged alkali cellulose copper ammonia is 70-90 mPa.S.
Further, CS is used in the step a yellowing step2The addition amount of the alpha-methyl cellulose is 35-45% of the weight ratio of the alpha-methyl cellulose.
Furthermore, the denaturant in the step b is one or more selected from polyoxyethylene alkylphenol ether, polyoxyethylene alkylamine, polyoxyethylene, polyoxyalkylene glycol, polyethylene glycol, aromatic alcohol, polyol, diethylamine, dimethylamine, cyclohexylamine and alkylamine polyethylene glycol, preferably more than two of the denaturants are used as a mixed denaturant.
Further, the index of the spinning solution in the step b is as follows: the weight ratio of the first fiber: 6.5 to 10.0 percent of alkali, 6.0 to 10.0 percent of alkali, 35 to 100S of viscosity and 5 to 20ml of ripening degree.
Further, the flame retardant auxiliary agent is a silane coupling agent and/or a polyol crosslinking agent. The silane coupling agent has a chemical formula of RSiX3, wherein R represents amino, vinyl and epoxy, the groups have strong reaction capability with different matrix resins, and X represents hydrolyzable alkoxy, such as methoxy and ethoxy. The polyalcohol crosslinking agent is polyethylene glycol, polyglycerol, and trimethylolpropane.
Further, the flame retardant is an organosilane hydrolysis dispersion liquid. The chemical formula is [ MexOy· nSiO2]+[-CONH]Wherein Me represents a metal ion and the metal ion is Ti4+、Ca2+、Li+、K+、Na+Metal ions are combined on a cellulose main chain to form a space network structure.
Further, the spinning bath consists of: 60-90 g/L of sulfuric acid, 40-80 g/L of zinc sulfate, 100-160 g/L of sodium sulfate and 30-50 ℃ of temperature.
Further, in the step e, the negative draft of the nascent strand silk through a spray head is-50-60%, the draft of a spinning disc is 36-6%, and the draft of a plasticizing bath is 6-18%.
Further, the crosslinking curing process: the curing temperature is 85-99 ℃, the curing time is 10 +/-5 minutes, and the curing bath comprises the following components: soft water: t-4= 10-80%: 80-20 percent of the total flame retardant cross-linking curing agent, T-4 is a novel flame retardant cross-linking curing agent produced by Xinxiang Changchong chemical industry limited company, has the characteristics of lasting effect, no toxicity and no pollution, can further improve the bonding strength of the flame retardant and the fiber, greatly improves the water washing resistance effect of the prepared viscose fiber, and still has good flame retardant effect after being washed and used for many times.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
1. the high-wet-modulus silicon nitrogen flame-retardant viscose fiber prepared by the method has high dry and wet strength, good spinnability and excellent physical and mechanical properties, the dry breaking strength is more than or equal to 2.6CN/dtex, the dry breaking elongation is 13-16%, and the wet breaking strength is more than or equal to 1.5 CN/dtex.
2. The high-wet-modulus silicon nitrogen flame-retardant viscose fiber prepared by the method has the limiting oxygen index of more than or equal to 30 percent and the wet breaking modulus of 0.35-0.55 CN/dtex, and can be applied to the fields of high-grade textile and garment materials with flame-retardant requirements and the like.
3. In the preparation process, the flame-retardant auxiliary agent and the viscose are mixed and pre-reacted, so that the activity and the stability of the combination of the viscose and the flame retardant are improved.
4. In the preparation process, after the flame retardant auxiliary agent and the viscose are pre-reacted, the viscose and the flame retardant are subjected to graft polymerization, a spinning process of low-acid, low-sodium and high-zinc coagulation bath ratio and high-magnification stepped drafting is adopted during spinning forming, and crosslinking curing treatment is carried out during post-treatment, so that the preparation of the high-wet-modulus silicon-nitrogen flame-retardant fiber is completed, the combination efficiency of the flame retardant and the viscose is improved, the flame retardant effect of the fiber is further improved, and the flame retardant time of the fiber is prolonged.
5. The flame-retardant viscose fiber prepared by the invention has the characteristics of physical and mechanical properties and high wet modulus of the flame-retardant fiber.
6. In the preparation process, the denaturant is blended and added into the spinning solution prepared from the pulp with higher polymerization degree, then the flame-retardant auxiliary agent and the flame retardant are added into the spinning solution by adopting the step-by-step injection technology before spinning, and the denaturant and the flame-retardant auxiliary agent are combined for use, so that the spinning quality is relatively stable in the use process of downstream customers of the prepared flame-retardant high-wet-modulus fiber, the generation of spinning burrs is reduced, and the loss of equipment is reduced.
7. In the preparation process, the flame-retardant auxiliary agent and the viscose undergo pre-reaction and graft polymerization, so that the phenomenon of poor flame-retardant effect of the fiber caused by the flame retardant and the viscose is avoided, the phenomenon of 'same batch and different effects' is avoided, and the quality uniformity of the prepared flame-retardant viscose fiber is improved.
8. Due to the cross-linking curing reaction of the post-treatment, the bonding strength of the flame retardant and the fiber is further improved, the water washing resistance effect of the prepared viscose fiber is greatly improved, and the viscose fiber still has a good flame retardant effect after being washed for many times.
Detailed Description
Example 1
1. Preparing a spinning solution:
alpha cellulose with a polymerization degree of about 830Mixing five batches of cotton and wood pulp with the content of more than or equal to 95 percent in any proportion, fully mixing the mixture with an immersion alkali liquor, immersing the mixture in 238 +/-1 g/L sodium hydroxide alkali solution at 50 ℃ for 60min, and squeezing the mixture to prepare alkali cellulose; the alkali cellulose is subjected to crushing and aging treatment, wherein the aging temperature is as follows: aging for 1h at 22 ℃; then with CS2Mixing and carrying out yellowing reaction at the temperature of 18 ℃ for 60min, wherein the addition of carbon disulfide to the alpha-cellulose is 34% during the yellowing reaction to generate cellulose xanthate; the cellulose xanthate is primarily dissolved in dilute alkali solution to obtain spinning solution, and denaturant with the content of 4.5 percent of alpha-cellulose is added in the later stage of dissolution, wherein the denaturant comprises 3 percent of PEG and 1.5 percent of hydroxyethyl amine; and (4) sequentially carrying out post-dissolution, three-pass filtration, defoaming and ripening on the spinning solution to obtain the spinning solution. Spinning stock solution index: fiber A: 8.58% by weight of an alkali content of 6.2%, a degree of esterification of 57, and a viscosity of 82S.
2. Two pre-spinning injections:
the temperature of the spinning solution is regulated to 25 ℃ through a heat exchanger, an epoxy silane coupling agent with the flame retardant of 25 percent is injected into the spinning solution through a one-pass pre-spinning injection system, and after the pre-reaction of the epoxy silane coupling agent and the spinning solution through a static mixer, the flame retardant with the flame retardant of 48 weight percent is injected through a two-pass pre-spinning injection system. Wherein the flame retardant contains titanium oxide, calcium oxide, silicon dioxide and amide. The mixture enters a viscose mixer for mixing after passing through a dynamic mixer and a static mixer, and is subjected to graft polymerization reaction for 30 minutes in the mixer and then is subjected to spinning.
3. Spinning:
extruding a spinning stock solution from a nozzle in a spinning machine to react with a coagulating bath to obtain a nascent fiber tow; 86 +/-1 g/L of coagulating bath components of sulfuric acid, 58 +/-0.5 g/L of zinc sulfate, 125 +/-10 g/L of sodium sulfate and reaction temperature: 38 +/-1 ℃ and the length of the silk strip immersion bath: 800 mm; the diameter of the annular combined spinning nozzle is 0.055 mm; the temperature of the second bath is 96 +/-2 ℃; the concentration of the sulfuric acid in the two baths is 30 +/-5 g/L.
4. Drawing and post-treatment:
drafting the as-spun fiber tows by a 47.5 percent spray head, drafting by a 38 percent spinning disc, drafting by an 8 percent plasticizing bath and drafting by a-1 percent retraction gradient, performing plasticizing shaping, and then performing cutting and post-treatment, wherein the post-treatment process comprises pickling, curing and crosslinking, washing and oiling; and drying to obtain the high wet modulus flame-retardant fiber.
Washing with water: the pH value is 8.5, and the temperature is 60-80 ℃.
And (3) crosslinking and curing: temperature 88 ± 1 ℃, curing time 8 minutes, curing bath composition: soft water: t-4= 60%: 40 percent of
Oil bath: the pH value is 5-6, the temperature is 65 ℃, and the concentration is 6 g/L.
The finished product index of the high-strength regenerated cellulose fiber prepared by the process is as follows: nominal titer of 1.67dtex, dry strength of 2.67CN/dtex, dry elongation at break of 13.5%, wet strength at break of 1.71CN/dtex, wet modulus at break of 0.45CN/dtex, limiting oxygen index of 31%.
Example 2
1. Preparing a spinning solution:
mixing five batches of cotton and wood pulp with the polymerization degree of about 1000 and the alpha cellulose content of more than or equal to 95 percent in any proportion, fully mixing the mixture with dipping alkali liquor, and squeezing the mixture after dipping to prepare alkali cellulose; crushing the alkali cellulose, and carrying out aging treatment at the aging temperature of 26 ℃ for 120 min; then with CS2Mixing and carrying out yellowing reaction at the temperature of 19 ℃ for 65min, wherein the addition of carbon disulfide to the methyl fiber is 36% during the yellowing reaction to generate cellulose xanthate; primarily dissolving cellulose xanthate in dilute alkali solution to obtain spinning solution, and adding 3% of denaturant for methyl cellulose in the later stage of dissolution, wherein the denaturant comprises 2% of polyoxyethylene alkylphenol ether and 1% of cyclohexylamine; and (4) sequentially carrying out post-dissolution, three-pass filtration, defoaming and ripening on the spinning solution to obtain the spinning solution. Spinning stock solution index: fiber A: 9.1% by weight of an alkali content of 7.5%, a degree of esterification of 62, and a viscosity of 90S.
2. Two pre-spinning injections:
the temperature of the spinning solution is adjusted to 20 ℃ through a heat exchanger, trimethylolpropane with the flame retardant of 35 percent is injected into the spinning solution through a one-pass pre-spinning injection system, and the flame retardant with the para-methyl fiber content of 40 percent by weight is injected through a two-pass pre-spinning injection system after the trimethylolpropane is mixed and pre-reacted through a static mixer. Wherein the flame retardant contains titanium oxide, calcium oxide, silicon dioxide and amide. The mixture enters a viscose mixer for mixing after passing through a dynamic mixer and a static mixer, and is subjected to graft polymerization reaction for 100 minutes in the mixer and then is subjected to spinning.
3. Spinning:
extruding a spinning stock solution from a nozzle in a spinning machine to react with a coagulating bath to obtain a nascent fiber tow; 75 +/-1 g/L of coagulating bath components of sulfuric acid, 65 +/-1 g/L of zinc sulfate, 146 +/-10 g/L of sodium sulfate and reaction temperature: 42 +/-1 ℃. The remaining spinning conditions were the same as in example 1.
4. Drawing and post-treatment:
drafting the as-spun fiber tows by a 40.4% spray head, drafting by a 45% spinning disc, drafting by a 12% plasticizing bath and drafting by a-0.5% retraction gradient, cutting and post-treating after plasticizing and shaping, wherein the post-treatment process comprises pickling, curing and crosslinking, washing and oiling; and drying to obtain the high wet modulus flame-retardant fiber.
And (3) crosslinking and curing: temperature 95 ± 2 ℃, curing time 10 minutes, curing bath composition: soft water: t-4= 50%: 50 percent;
the finished product index of the high-strength regenerated cellulose fiber prepared by the process is as follows: the dry strength is 2.83CN/dtex, the dry elongation at break is 14.2 percent, the wet breaking strength is 1.74CN/dtex, the wet modulus at break is 0.49CN/dtex, and the limiting oxygen index is 32 percent.
Example 3
1. Preparing a spinning solution:
mixing five batches of cotton and wood pulp with polymerization degree of 1380 and alpha cellulose content of more than or equal to 95% in any proportion, fully mixing with dipping alkali liquor, dipping for 70min, and squeezing to obtain alkali cellulose; the alkali cellulose is subjected to crushing and aging treatment, wherein the aging temperature is as follows: aging at 29 deg.C for 210 min; then with CS2Mixing and carrying out yellowing reaction, wherein the adding amount of carbon disulfide to the methyl fiber is 40% during the yellowing reaction, and cellulose xanthate is generated; cellulose xanthate is primarily dissolved in dilute alkali solution to obtain spinning solution, and a denaturant with the content of 2.5 percent of alpha-cellulose is added in the later stage of dissolution, wherein the denaturant comprises 1.5 percent of polyoxyalkylene glycol and 1.0 percent of diethylamine; and (4) sequentially carrying out post-dissolution, three-pass filtration, defoaming and ripening on the spinning solution to obtain the spinning solution. Spinning stock solution index: fiber A: 9.8% by weight of alkali, 8.9% by weight of alkali, 68% by weight of esterification degree and 85S by weight of viscosity.
2. Two pre-spinning injections:
the temperature of the spinning solution is regulated to 25 ℃ through a heat exchanger, epoxy silane coupling agent with the flame retardant of 40 percent is injected into the spinning solution through a one-pass pre-spinning injection system, and after the epoxy silane coupling agent is mixed and pre-reacted through a static mixer, the flame retardant with the methyl fiber content of 38 percent by weight is injected through a two-pass pre-spinning injection system. Wherein the flame retardant contains titanium oxide, calcium oxide, silicon dioxide and amide. The mixture enters a viscose mixer for mixing after passing through a dynamic mixer and a static mixer, and is subjected to graft polymerization reaction for 160 minutes in the mixer and then is subjected to spinning.
3. Spinning:
extruding a spinning stock solution from a nozzle in a spinning machine to react with a coagulating bath to obtain a nascent fiber tow; the coagulating bath components comprise 64g/L of sulfuric acid, 75 +/-1 g/L of zinc sulfate, 155 +/-10 g/L of sodium sulfate and the reaction temperature: 47 +/-1 ℃. The remaining spinning conditions were the same as in example 1.
4. Drawing and post-treatment:
drafting the as-spun fiber tows by a 27.2% spray head, drafting by a 52% spinning disc, drafting by a 16% plasticizing bath and drafting by a-1% retraction gradient, performing plasticizing shaping, and then performing cutting and post-treatment, wherein the post-treatment process comprises pickling, curing and crosslinking, washing and oiling; and drying to obtain the high wet modulus flame-retardant fiber.
And (3) crosslinking and curing: temperature 98 ± 1 ℃, curing time 14 minutes, curing bath composition: soft water: t-4= 40%: 60 percent;
the finished product index of the high-strength regenerated cellulose fiber prepared by the process is as follows: the dry strength is 2.89CN/dtex, the dry elongation at break is 15.6 percent, the wet breaking strength is 1.80CN/dtex, the wet modulus at break is 0.52CN/dtex, and the limiting oxygen index is 33 percent.
From the flame-retardant high wet modulus viscose fibers prepared in examples 1 to 3, it is understood that the physical comprehensive index of the silicon nitrogen-based flame-retardant high wet modulus viscose fiber prepared in example 3 is the most excellent.
Comparative example 4
In order to further verify the influence of the relevant processes on the prepared fiber in the preparation process of the invention, the preparation method of example 3 is adopted, and the cross-linking curing process in the steps of drafting and post-treatment is omitted, specifically:
1. preparing a spinning solution:
mixing five batches of cotton and wood pulp with polymerization degree of 1380 and alpha cellulose content of more than or equal to 95% in any proportion, fully mixing with dipping alkali liquor, dipping for 70min, and squeezing to obtain alkali cellulose; the alkali cellulose is subjected to crushing and aging treatment, wherein the aging temperature is as follows: aging at 29 deg.C for 210 min; then with CS2Mixing and carrying out yellowing reaction, wherein the adding amount of carbon disulfide to the methyl fiber is 40% during the yellowing reaction, and cellulose xanthate is generated; cellulose xanthate is primarily dissolved in dilute alkali solution to obtain spinning solution, and a denaturant with the content of 2.5 percent of alpha-cellulose is added in the later stage of dissolution, wherein the denaturant comprises 1.5 percent of polyoxyalkylene glycol and 1.0 percent of diethylamine; and (4) sequentially carrying out post-dissolution, three-pass filtration, defoaming and ripening on the spinning solution to obtain the spinning solution. Spinning stock solution index: fiber A: 9.8% by weight of alkali, 8.9% by weight of alkali, 68% by weight of esterification degree and 85S by weight of viscosity.
2. Two pre-spinning injections:
the temperature of the spinning solution is regulated to 25 ℃ through a heat exchanger, epoxy silane coupling agent with the flame retardant of 40 percent is injected into the spinning solution through a one-pass pre-spinning injection system, and after the epoxy silane coupling agent is mixed and pre-reacted through a static mixer, the flame retardant with the methyl fiber content of 38 percent by weight is injected through a two-pass pre-spinning injection system. Wherein the flame retardant contains titanium oxide, calcium oxide, silicon dioxide and amide. The mixture enters a viscose mixer for mixing after passing through a dynamic mixer and a static mixer, and is subjected to graft polymerization reaction for 160 minutes in the mixer and then is subjected to spinning.
3. Spinning:
extruding a spinning stock solution from a nozzle in a spinning machine to react with a coagulating bath to obtain a nascent fiber tow; coagulating bath components sulfuric acid (64 +/-1) g/L, zinc sulfate (75 +/-1) g/L, sodium sulfate (155 +/-10) g/L and reaction temperature: (47. + -. 1). degree.C. The remaining spinning conditions were the same as in example 1.
4. Drawing and post-treatment:
drafting the as-spun fiber tows by a 27.2% spray head, drafting by a 52% spinning disc, drafting by a 16% plasticizing bath and drafting by a-1% retraction gradient, performing plasticizing shaping, and then performing cutting and post-treatment, wherein the post-treatment process comprises pickling, washing and oiling; and drying to obtain the high wet modulus flame-retardant fiber.
The finished indexes of the flame-retardant high-strength regenerated cellulose fiber prepared by the process are as follows: the dry strength is 2.35CN/dtex, the dry elongation at break is 13.8 percent, the wet breaking strength is 1.60CN/dtex, the wet modulus at break is 0.49CN/dtex, and the limiting oxygen index is 31 percent.
In the implementation process of the comparative example 4, the cross-linking curing process in the drawing and post-treatment steps is omitted, so that the physical index of the prepared flame-retardant high-strength regenerated cellulose fiber is obviously reduced compared with the physical index of the flame-retardant high-strength regenerated cellulose fiber prepared in the embodiment 3 of the invention, particularly the dry breaking strength is obviously reduced, which shows that the cross-linking curing process can obviously improve the dry breaking strength of the flame-retardant fiber, particularly the silicon nitrogen flame-retardant high-wet-modulus fiber.
In the preparation and use processes of the flame-retardant high-wet-modulus viscose fiber, the invention finds that the crosslinking and curing process can not only improve the dry breaking strength of the silicon-nitrogen flame-retardant high-wet-modulus viscose fiber, but also improve the adhesion of the silicon-nitrogen flame retardant to the fiber, so that the prepared fiber still has good flame retardant property after being washed for many times, and in order to further verify and find out the optimal production process, the following tests are carried out:
the test contents are as follows: the company washes the prepared silicon nitrogen flame-retardant high wet modulus viscose fiber and detects the ignition residue;
sample preparation: 50 equal parts of the viscose fibers prepared in the embodiments 1, 2, 3 and the comparative example 4 are prepared respectively for standby;
the test method comprises the following steps:
the phosphate-free washing powder comprises the following components: the fiber =0.25:100, water is permeated through the fiber, the fiber is washed by hand for 15min each time, the fiber is dehydrated for 3min, then the same amount of clean water in the last time is added, the fiber is washed by hand for 3min, the fiber is dehydrated for 3min, the fiber is dried after the dehydration is finished, the drying temperature is 120 ℃, the drying time is 2h, and the sample mass is weighed;
firing residue: burning the dried fiber in a high-temperature furnace at 780-800 ℃ for 2.5h, and weighing the burning residual mass;
by adopting the washing method, the samples (examples 1, 2 and 3 and comparative example 4) are continuously washed for 50 times, and burning residue detection is carried out after each 10 times of washing, and specific detection results are shown in Table 1
TABLE 1
As can be seen from table 1, the silicon nitrogen based flame retardant high wet modulus viscose fiber prepared in embodiments 1 to 3 of the present invention adopts a cross-linking curing process, and the ignition residue of the fiber after ignition is high, which proves that after many times of washing, the loss of the flame retardant effective component in the fiber is low, and thus the duration of the flame retardant effect is long.
The flame-retardant viscose fiber prepared in the comparative example 4 omits a cross-linking and curing process in the drawing and post-treatment steps, and the ignition residues are low, namely, the loss of the flame-retardant effective components in the fiber is proved to be large after multiple times of washing, so that the flame-retardant viscose fiber prepared in the comparative example 4 has short duration of flame-retardant effect and poor washing resistance.
In the prior production process, a spinning solution is added with a flame retardant additive and a flame retardant, the flame retardant additive and viscose are mixed and pre-reacted in advance to improve the activity and the stability of the combination of the viscose and the flame retardant, then the viscose and the flame retardant are subjected to graft polymerization reaction, so that spinning burrs are often generated in the downstream spinning process although the retention of the flame retardant in the fiber is improved, and the loss and the abrasion of equipment are increased, in the preparation process of the invention, a denaturant is blended in a spinning stock solution prepared from pulp with higher polymerization degree, then the flame retardant additive and the flame retardant are added in the spinning solution by adopting a step-by-step pre-spinning injection technology, and the denaturant and the flame retardant additive are used in a combined manner, so that the spinning quality is more stable in the use process of downstream customers of the prepared flame-retardant high-wet modulus fiber, the generation of the spinning burrs is reduced, and the loss of the equipment in the spinning process is reduced, the quality of the product is improved.
The above examples merely represent specific embodiments of the present invention and are not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (5)
1. The silicon nitrogen flame-retardant high wet modulus viscose fiber is characterized in that: the dry breaking strength of the fiber is more than or equal to 2.6CN/dtex, the wet breaking strength is more than or equal to 1.5CN/dtex, the limiting oxygen index is more than or equal to 30 percent, and the wet breaking modulus is more than or equal to 0.35 CN/dtex; the preparation method of the silicon-nitrogen flame-retardant high-wet-modulus viscose fiber comprises the following steps: preparing cellulose xanthate; preparing a spinning solution; a second injection step before spinning; the second injection step before spinning: adding a flame-retardant auxiliary agent and a flame retardant into the prepared spinning solution in sequence for mixing;
the preparation method comprises the following steps: carrying out yellowing reaction on cotton and/or wood pulp with the polymerization degree of 800-1400 to generate cellulose xanthate;
the spinning solution preparation step comprises: dissolving the prepared cellulose xanthate in an alkali solution, adding a denaturant to obtain a spinning solution, and preparing the spinning solution;
the method also comprises the steps of drawing and post-processing, wherein the post-processing process comprises the step of crosslinking and curing; the cross-linking and curing step is to perform cross-linking and curing reaction on the cut fiber in a curing bath;
the crosslinking curing step, the curing temperature: curing time at 85-99 ℃ is as follows: 10 ± 5 minutes, the curing bath consisting of, soft water: t-4= 10-80%: 90-20%;
the flame retardant additive is 20-50wt% of the flame retardant, the flame retardant additive is 20-50wt% of the content of the methyl fiber in the spinning solution, the flame retardant additive is a silane coupling agent and/or a polyol crosslinking agent, the flame retardant is an organosilane hydrolysis dispersion liquid, and the chemical formula of the organosilane hydrolysis dispersion liquid is [ MexOy·nSiO2]+[-CONH]Wherein Me represents a metal ion, the metal ion being Ti4+,One or more of Ca2+, Li +, K + and Na +;
the addition amount of the denaturant is 2.5-4.5%, and the denaturant is one or more of polyoxyethylene alkylphenol ether, polyoxyethylene alkylamine, polyoxyethylene, polyoxyalkylene glycol, polyethylene glycol, aromatic alcohol, diethylamine, dimethylamine, cyclohexylamine and alkylamine polyethylene glycol.
2. The viscose fiber with silicon nitrogen flame retardant and high wet modulus as claimed in claim 1, wherein: the drafting comprises nozzle drafting, spinning disc drafting and plasticizing bath drafting, wherein the nozzle drafting is-50-60%, the spinning disc drafting is 36-6%, and the plasticizing bath drafting is 6-18%.
3. The viscose fiber with silicon nitrogen flame retardant and high wet modulus as claimed in claim 1, wherein: the method further comprises a spinning step; the spinning bath in the spinning step consists of: 60-90 g/L of sulfuric acid, 40-80 g/L of zinc sulfate, 100-160 g/L of sodium sulfate and 30-50 ℃ of temperature.
4. The viscose fiber with silicon nitrogen flame retardant and high wet modulus as claimed in claim 1, wherein: the step of preparing the cellulose xanthate comprises an ageing step, wherein the ageing temperature is 20-30 ℃, the ageing time is 1-4 hours, and the viscosity of the aged alkali cellulose copper ammonia is 70-90 mPa.S.
5. The viscose fiber with silicon nitrogen flame retardant and high wet modulus as claimed in claim 1, wherein: the indexes of the spinning solution are as follows: the weight ratio of the first fiber: 6.5 to 10.0% by weight of alkali, 6.0 to 10.0% by weight of alkali, 35 to 100S in viscosity, 5 to 20ml in degree of ripening, and CS in the yellowing step2The addition amount of the alpha-methyl cellulose is 35-45% of the weight ratio of the alpha-methyl cellulose.
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