CN112746347A - Preparation method of halogen-free flame-retardant polyacrylonitrile fiber - Google Patents
Preparation method of halogen-free flame-retardant polyacrylonitrile fiber Download PDFInfo
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- CN112746347A CN112746347A CN201911057164.7A CN201911057164A CN112746347A CN 112746347 A CN112746347 A CN 112746347A CN 201911057164 A CN201911057164 A CN 201911057164A CN 112746347 A CN112746347 A CN 112746347A
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides a preparation method of halogen-free flame-retardant polyacrylonitrile fiber. The method mainly comprises the following steps: heating and melting the halogen-free phosphorus-nitrogen-containing flame retardant, then stirring and blending the halogen-free phosphorus-nitrogen-containing flame retardant with polyacrylonitrile spinning solution, and carrying out cross-linking hydrolysis after wet spinning to obtain the halogen-free phosphorus-nitrogen-containing flame retardant. The preparation method of the invention ensures that the halogen-free organic phosphorus nitrogen flame retardant can be well, uniformly and stably dispersed in the spinning solution, thereby effectively avoiding the generation of hole blockage during spinning and greatly prolonging the period of replacing the spray nozzle during spinning. Meanwhile, after the hot drawing process in the spinning process of the flame-retardant acrylic fiber, the chemical modification of crosslinking and alkaline hydrolysis is further carried out on the surface of the fiber, so that the flame retardance LOI of the prepared acrylic fiber is not less than 26%, and the moisture absorption of the acrylic fiber is improved.
Description
Technical Field
The invention relates to the technical field of acrylic fiber manufacturing, in particular to a method for preparing halogen-free flame-retardant polyacrylonitrile fiber by using a sodium thiocyanate aqueous solution as a spinning solvent and adopting a wet spinning process.
Background
Fire caused by the combustion of chemical fiber textile products has become one of the major disasters of the current society, so the research and development of flame-retardant textile products has become an urgent requirement for people, and the flame-retardant textile products are more and more concerned by people.
Although polyacrylonitrile fiber has many advantages and wide application, and is a synthetic fiber variety widely used in China and other countries, polyacrylonitrile fiber is a flammable fiber, has a Limiting Oxygen Index (LOI) of only 18%, and emits cyanide and other substances with high toxicity when burning. Therefore, the research and development of the flame-retardant polyacrylonitrile polymer and the fiber thereof are very important. Hitherto, the industrial textile flame-retardant acrylic products at home and abroad are mainly nitrile-vinyl chloride polymers manufactured by a copolymerization flame-retardant method, which are obtained by copolymerizing a halogen-containing monomer and acrylonitrile or adding an antimony compound into a copolymer system as a synergist, and then spinning to obtain the flame-retardant acrylic fibers, wherein the content of copolymerized flame-retardant monomer vinyl halide in the flame-retardant acrylic fibers reaches 40% or more, although the flame-retardant fibers have a good flame-retardant effect, the flame-retardant fibers have a large smoke generation amount during combustion, and toxic hydrogen halide gas, corrosive halide and the like are released in the combustion process due to the existence of halogen components, so that environmental pollution is caused. With the continuous upgrading of environmental protection laws and regulations of various countries, the application of the halogen-containing flame retardant on the acrylic fiber is limited to a certain extent, so that the research on the halogen-free flame-retardant polyacrylonitrile polymer or the flame-retardant acrylic fiber is promoted. The blending flame retardant method is adopted, and the relevant reports and documents about the spinning of the flame retardant acrylic fiber by directly adding the halogen-free flame retardant into the spinning solution are rare, and especially for the spinning route taking the NaSCN aqueous solution as the solvent, the industrial reports are not found due to the difficulty in selecting the proper blending flame retardant. Although the blending method is inferior to the copolymerization method in the flame retardant effect or certain physical and mechanical properties of the flame retardant acrylic fibers, the method has the advantages of simple process, wide application range and flexible production, is favorable for the production of various modified products, and is a flame retardant fiber preparation method with a relatively promising prospect because the original production line and equipment of the acrylic fibers are not required to be changed.
The blended flame-retardant acrylic fiber is not like the copolymerized flame-retardant acrylic fiber which improves the flame-retardant effect by increasing the content of the copolymerized flame-retardant monomer component, but for the blended flame-retardant acrylic fiber, the content of the flame retardant can not be too high, otherwise, the forming and the performance of the fiber can be seriously influenced. Therefore, an efficient flame retardant or flame retardant synergistic assistant must be selected to reduce the amount of the flame retardant. Most of the fire retardants selected for preparing the blended halogen-free flame retardant acrylic fibers at present are solid powder.
In the existing industrial textile flame-retardant acrylic fiber, the preparation is to use halogen-containing monomer and acrylonitrile to copolymerize or add antimony compound as synergist to obtain flame-retardant polyacrylonitrile polymer, and then to prepare the flame-retardant acrylic fiber through spinning. With the upgrading established by environmental protection laws and regulations, the application of the halogen-containing flame retardant on the acrylic fiber is limited to a certain extent, thereby promoting the research of the halogen-free flame-retardant polyacrylonitrile polymer or the flame-retardant acrylic fiber.
Disclosure of Invention
The invention provides a preparation method of halogen-free flame-retardant polyacrylonitrile fiber. The preparation method of the invention ensures that the halogen-free organic phosphorus nitrogen flame retardant can be well, uniformly and stably dispersed in the spinning solution, thereby effectively avoiding the generation of hole blockage during spinning and greatly prolonging the period of replacing the spray nozzle during spinning. Meanwhile, after the hot drawing process in the spinning process of the flame-retardant acrylic fiber, the chemical modification of crosslinking and alkaline hydrolysis is further carried out on the surface of the fiber, so that the flame retardance LOI of the prepared acrylic fiber is not less than 26%, and the moisture absorption of the acrylic fiber is improved.
The technical scheme of the invention is as follows:
the invention provides a preparation method of halogen-free flame-retardant polyacrylonitrile fiber, which comprises the following steps:
step 1: heating the halogen-free phosphorus-nitrogen-containing flame retardant to melt, heating to above 40 ℃, continuously stirring for more than 30 minutes until the halogen-free phosphorus-nitrogen-containing flame retardant is completely melted to be transparent and light yellow liquid for later use;
step 2: under the stirring state, uniformly mixing the liquid halogen-free phosphorus-nitrogen-containing flame retardant obtained after melting in the step (1) with the polyacrylonitrile spinning solution according to the weight ratio of 20-40:60-80, stirring at the rotating speed of 800-;
or the liquid halogen-free phosphorus-nitrogen-containing flame retardant obtained after melting in the step (1) is subjected to online blending with polyacrylonitrile spinning solution in a weight ratio of 20-40:60-80 in an online injection manner before spinning, the feeding ratio is automatically cascade-controlled by DSC, and the cascade ratio is adjusted in a ratio of 0.3-0.45:1, so as to obtain blended flame-retardant spinning solution;
and step 3: and (3) standing and defoaming the blended flame-retardant spinning solution obtained in the step (2) at 85 ℃ in vacuum for 15 minutes with the vacuum degree of 100KPa, filtering, performing wet spinning, performing 6-8 times of thermal drafting in the spinning process, performing crosslinking treatment for 1-1.5 hours in hydrazine hydrate, amine or guanidine crosslinking agent solution at the treatment temperature of 85-95 ℃, and then performing hydrolysis treatment by using NaOH solution at the temperature of 85-90 ℃ for 10-15 minutes to obtain the halogen-free flame-retardant polyacrylonitrile fiber.
Further, the halogen-free phosphorus-nitrogen-containing flame retardant in the step (1) is one or a mixture of more than two of vinyl phosphonic acid, methyl vinyl phosphonate, ethyl vinyl phosphonate, methyl allyl phosphate, ethyl allyl phosphate and hydroxyethyl triacrylate.
Further, the weight ratio of the halogen-free phosphorus-nitrogen-containing flame retardant in the step (2) to the polyacrylonitrile spinning solution is 25-35: 65-75.
Further, the polyacrylonitrile spinning solution in the step (2) is prepared by a two-step method to obtain:
feeding polyacrylonitrile slurry with the concentration of 34 wt% and the temperature of 50 ℃ and NaSCN solvent with the concentration of 58 wt% and the temperature of 85 ℃ into a high-shear dissolving machine for mixing according to a feeding proportion, wherein the feeding proportion is automatically controlled by DSC in a cascade mode, and the cascade ratio is adjusted according to the total solid of discharged spinning stock solution and is generally controlled to be 1: 1.4-1.6; the total solid of the spinning solution is controlled to be 11.8 +/-0.05 percent.
Further, the polyacrylonitrile in the polyacrylonitrile spinning solution in the step (2) is copolymerized by the following monomers in parts by weight: based on 100 parts, 85-92 parts of acrylonitrile monomer, 8-14 parts of methyl acrylate and 0.1-2.0 parts of sodium methallyl sulfonate.
Further, the polyacrylonitrile in the polyacrylonitrile spinning solution in the step (2) is copolymerized by the following monomers in parts by weight: 90 parts of acrylonitrile monomer, 8 parts of methyl acrylate and 2 parts of sodium methallyl sulfonate by 100 parts.
Further, the concentration of the hydrazine hydrate, guanidine or amine crosslinking agent solution in the step (3) is 10-30 wt%; the concentration of the NaOH solution is 7-15 wt%.
The invention also provides the halogen-free flame-retardant polyacrylonitrile fiber prepared by the preparation method.
The invention has the beneficial effects that:
the invention selects the liquid halogen-free organic phosphorus nitrogen flame retardant at the spinning temperature (not less than 83 ℃), and the key is that the flame retardant can be well, uniformly and stably dispersed in the spinning solution, does not aggregate and deposit, so that the filtration of the blended flame-retardant spinning solution is better than that of the flame retardant adopting solid powder (the flame retardant adopting solid powder needs surface treatment and is easy to aggregate otherwise) under the same content condition, thereby effectively avoiding the generation of the hole blocking phenomenon during spinning and greatly prolonging the spinning period; the fiber is insoluble in NaSCN solvent and water, so that the loss of a flame retardant in the spinning process is avoided, the flame retardant durability of the fiber is improved, and the solvent is prevented from being polluted and the solvent recovery cost is prevented from increasing; the polyacrylonitrile fiber has good compatibility with polyacrylonitrile, can improve the dispersibility of the polyacrylonitrile fiber in spinning solution on one hand, and can reduce the negative influence on the physical and mechanical properties of the polyacrylonitrile fiber on the other hand.
According to the invention, after the hot drawing process in the spinning process of the flame-retardant acrylic fiber, a chemical modification process of firstly crosslinking and then hydrolyzing is inserted into the fiber surface, and the blending and the modification are innovatively and organically combined together, so that the acrylic fiber is endowed with a flame-retardant effect (LOI is more than or equal to 26%) and the hygroscopicity of the fiber is effectively improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
Step 1: heating the halogen-free phosphorus-nitrogen-containing flame retardant vinylphosphonic acid to melt, heating to over 85 ℃, and continuously stirring for over 30 minutes until the mixture is completely melted to be transparent and light yellow liquid.
Step 2: under the stirring state, uniformly mixing the liquid halogen-free phosphorus-nitrogen-containing flame retardant vinylphosphonic acid obtained by melting in the step (1) and polyacrylonitrile spinning solution according to the weight ratio of 30:70, stirring at the rotating speed of 1000r/min for 30 minutes to obtain blended flame-retardant spinning solution;
wherein, the polyacrylonitrile spinning solution is prepared by a two-step method:
feeding 34 wt% polyacrylonitrile slurry from a storage tank, 50 deg.C NaSCN solvent from a concentrated solvent storage tank at 85 deg.C into a high shear dissolver according to the feeding proportion, wherein the feeding proportion is automatically controlled by DSC in cascade, and the cascade ratio is regulated according to the total solid content (11.8 + -0.05%) of the discharged spinning solution, and is generally controlled at 1: 1.53;
the polyacrylonitrile is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts: 90 parts of acrylonitrile monomer, 8 parts of methyl acrylate and 2 parts of sodium methallyl sulfonate.
And step 3: and (3) standing and defoaming the blended flame-retardant spinning solution obtained in the step (2) at 85 ℃ in vacuum for 15 minutes with the vacuum degree of 100KPa, filtering, performing wet spinning, performing 6-8 times of hot drafting in the spinning process, performing crosslinking treatment for 1 hour in a hydrazine hydrate crosslinking agent solution with the concentration of 30 wt%, performing hydrolysis treatment at 85 ℃ by using a NaOH solution with the concentration of 10 wt%, and performing hydrolysis treatment for 15 minutes to obtain the halogen-free flame-retardant polyacrylonitrile fiber.
Example 2
Step 1: heating and melting the halogen-free phosphorus-nitrogen-containing flame retardant (methyl vinylphosphonate and ethyl vinylphosphonate are mixed according to the mass ratio of 1: 2), heating to above 85 ℃, and continuously stirring for more than 30 minutes until the halogen-free phosphorus-nitrogen-containing flame retardant is completely melted to be transparent and light yellow liquid.
Step 2: under the stirring state, uniformly mixing the mixture of the liquid halogen-free phosphorus-nitrogen-containing flame retardant methyl vinylphosphonate and ethyl vinylphosphonate prepared in the step (1) and the polyacrylonitrile spinning solution according to the weight ratio of 35:65, stirring at the rotating speed of 1200r/min for 40 minutes to obtain a blended flame-retardant spinning solution;
wherein, the polyacrylonitrile spinning solution is prepared by a two-step method:
feeding 34 wt% polyacrylonitrile slurry from a storage tank, 50 deg.C NaSCN solvent from a concentrated solvent storage tank at 85 deg.C into a high shear dissolver according to the feeding proportion, wherein the feeding proportion is automatically controlled by DSC in cascade, and the cascade ratio is regulated according to the total solid content (11.8 + -0.05%) of the discharged spinning solution, and is generally controlled at 1: 1.53;
the polyacrylonitrile is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts: 90 parts of acrylonitrile monomer, 8 parts of methyl acrylate and 2 parts of sodium methallyl sulfonate.
And step 3: and (3) standing and defoaming the blended flame-retardant spinning solution obtained in the step (2) at 85 ℃ in vacuum for 15 minutes with the vacuum degree of 100KPa, filtering, performing wet spinning, performing 6-8 times of hot drafting in the spinning process, performing crosslinking treatment in an organic guanidine crosslinking agent solution for 1 hour at the treatment temperature of 90 ℃, performing hydrolysis treatment by using a 15 wt% NaOH solution at the temperature of 90 ℃, and performing treatment for 10 minutes to obtain the halogen-free flame-retardant polyacrylonitrile fiber.
Example 3
Step 1: heating and melting halogen-free phosphorus-nitrogen-containing flame retardant allyl methyl phosphate, heating to 42 ℃, and continuously stirring for more than 30 minutes until the halogen-free phosphorus-nitrogen-containing flame retardant allyl methyl phosphate is completely melted to be transparent and light yellow liquid.
Step 2: the liquid halogen-free phosphorus-nitrogen-containing flame retardant allyl methyl phosphate prepared in the step (1) is subjected to online blending with polyacrylonitrile spinning solution in a weight ratio of 25:75 by a high shear dissolving machine in an online injection mode before spinning, the feeding ratio is automatically controlled by DSC in a cascade mode, and the cascade ratio is adjusted to be 0.3-0.45:1 to obtain blended flame-retardant spinning solution;
wherein, the polyacrylonitrile spinning solution is prepared by a two-step method:
feeding 34 wt% polyacrylonitrile slurry from a storage tank, 50 deg.C NaSCN solvent from a concentrated solvent storage tank at 85 deg.C into a high shear dissolver according to the feeding proportion, wherein the feeding proportion is automatically controlled by DSC in cascade, and the cascade ratio is regulated according to the total solid content (11.8 + -0.05%) of the discharged spinning solution, and is generally controlled at 1: 1.53;
the polyacrylonitrile is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts: 90 parts of acrylonitrile monomer, 8 parts of methyl acrylate and 2 parts of sodium methallyl sulfonate.
And step 3: and (3) standing and defoaming the blended flame-retardant spinning solution obtained in the step (2) at 65 ℃ in vacuum for 15 minutes with the vacuum degree of 100KPa, filtering, performing wet spinning, performing 6-8 times of hot drafting in the spinning process, performing crosslinking treatment in an organic guanidine crosslinking agent solution for 1.5 hours at 95 ℃, performing hydrolysis treatment by using a 15 wt% NaOH solution at 90 ℃ for 10 minutes, and thus obtaining the halogen-free flame-retardant polyacrylonitrile fiber.
Example 4
Step 1: heating and melting the halogen-free phosphorus-nitrogen-containing flame retardant (methyl vinylphosphonate: ethyl allylphosphate in a mass ratio of 1: 2: 0.5), heating to 45 ℃, and continuously stirring for more than 30 minutes until the halogen-free phosphorus-nitrogen-containing flame retardant is completely melted to be transparent and light yellow liquid.
Step 2: under the stirring state, uniformly mixing the liquid halogen-free phosphorus-nitrogen-containing flame retardant prepared in the step (1) with the polyacrylonitrile spinning solution according to the weight ratio of 35:65, stirring at the rotating speed of 1500r/min for 50 minutes to obtain a blended flame-retardant spinning solution;
wherein, the polyacrylonitrile spinning solution is prepared by a two-step method:
feeding 34 wt% polyacrylonitrile slurry from a storage tank, 50 deg.C NaSCN solvent from a concentrated solvent storage tank at 85 deg.C into a high shear dissolver according to the feeding proportion, wherein the feeding proportion is automatically controlled by DSC in cascade, and the cascade ratio is regulated according to the total solid content (11.8 + -0.05%) of the discharged spinning solution, and is generally controlled at 1: 1.53;
the polyacrylonitrile is prepared by copolymerizing the following monomers in parts by weight, based on 100 parts: 90 parts of acrylonitrile monomer, 8 parts of methyl acrylate and 2 parts of sodium methallyl sulfonate.
And step 3: and (3) standing and defoaming the blended flame-retardant spinning solution obtained in the step (2) at 85 ℃ in vacuum for 15 minutes with the vacuum degree of 100KPa, filtering, performing wet spinning, performing 6-8 times of thermal drafting in the spinning process, performing crosslinking treatment in a hydrazine hydrate crosslinking agent solution for 1.5 hours at 85 ℃, performing hydrolysis treatment by using a 10 wt% NaOH solution at 85 ℃, and performing treatment for 15 minutes to obtain the halogen-free flame-retardant polyacrylonitrile fiber.
The performance test results of the halogen-free flame-retardant polyacrylonitrile fibers obtained in the above embodiments 1 to 4 are shown in table 1.
Table 1 examples 1-4 performance test evaluation
Remarking:
(1) the Limit Oxygen Index (LOI) test is referred to GB/T5454-1997 textile Combustion Performance test oxygen index method.
(2) The tests of the fineness, the breaking strength, the breaking elongation and the moisture regain of the fiber adopt GB/T14335-.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited to the embodiments disclosed, but is capable of numerous equivalents and substitutions, all of which are within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of halogen-free flame-retardant polyacrylonitrile fiber comprises the following steps:
step 1: heating the halogen-free phosphorus-nitrogen-containing flame retardant to melt, heating to above 40 ℃, continuously stirring for more than 30 minutes until the halogen-free phosphorus-nitrogen-containing flame retardant is completely melted to be transparent and light yellow liquid for later use;
step 2: under the stirring state, uniformly mixing the liquid halogen-free phosphorus-nitrogen-containing flame retardant obtained after melting in the step (1) with the polyacrylonitrile spinning solution according to the weight ratio of 20-40:60-80, stirring at the rotating speed of 800-;
or the liquid halogen-free phosphorus-nitrogen-containing flame retardant obtained after melting in the step (1) is subjected to online blending with polyacrylonitrile spinning solution in a weight ratio of 20-40:60-80 in an online injection manner before spinning, the feeding ratio is automatically cascade-controlled by DSC, and the cascade ratio is adjusted in a ratio of 0.3-0.45:1, so as to obtain blended flame-retardant spinning solution;
and step 3: and (3) standing and defoaming the blended flame-retardant spinning solution obtained in the step (2) at 85 ℃ in vacuum for 15 minutes with the vacuum degree of 100KPa, filtering, performing wet spinning, performing 6-8 times of thermal drafting in the spinning process, performing crosslinking treatment for 1-1.5 hours in hydrazine hydrate, amine or guanidine crosslinking agent solution at the treatment temperature of 85-95 ℃, and then performing hydrolysis treatment by using NaOH solution at the temperature of 85-90 ℃ for 10-15 minutes to obtain the halogen-free flame-retardant polyacrylonitrile fiber.
2. The preparation method of the halogen-free flame-retardant polyacrylonitrile fiber according to claim 1, characterized in that: the halogen-free phosphorus-nitrogen-containing flame retardant in the step (1) is one or a mixture of more than two of vinyl phosphonic acid, methyl vinyl phosphonate, ethyl vinyl phosphonate, allyl methyl phosphate, allyl ethyl phosphate and hydroxyethyl triacrylate.
3. The preparation method of the halogen-free flame-retardant polyacrylonitrile fiber according to claim 1, characterized in that: the weight ratio of the halogen-free phosphorus-nitrogen-containing flame retardant in the step (2) to the polyacrylonitrile spinning solution is 25-35: 65-75.
4. The preparation method of the halogen-free flame-retardant polyacrylonitrile fiber according to claim 1, characterized in that: the polyacrylonitrile spinning solution in the step (2) is prepared by a two-step method, and is prepared by the following steps:
feeding polyacrylonitrile slurry with the concentration of 34 wt% and the temperature of 50 ℃ and NaSCN solvent with the concentration of 58 wt% and the temperature of 85 ℃ into a high-shear dissolving machine for mixing according to a feeding proportion, wherein the feeding proportion is automatically controlled by DSC in a cascade mode, and the cascade ratio is adjusted according to the total solid of discharged spinning stock solution and is generally controlled to be 1: 1.4-1.6; the total solid of the spinning solution is controlled to be 11.8 +/-0.05 percent.
5. The preparation method of the halogen-free flame-retardant polyacrylonitrile fiber according to claim 1, characterized in that: the polyacrylonitrile in the polyacrylonitrile spinning solution in the step (2) is copolymerized by the following monomers in parts by weight: based on 100 parts, 85-92 parts of acrylonitrile monomer, 8-14 parts of methyl acrylate and 0.1-2.0 parts of sodium methallyl sulfonate.
6. The preparation method of the halogen-free flame-retardant polyacrylonitrile fiber according to claim 5, characterized in that: the polyacrylonitrile in the polyacrylonitrile spinning solution in the step (2) is copolymerized by the following monomers in parts by weight: 90 parts of acrylonitrile monomer, 8 parts of methyl acrylate and 2 parts of sodium methallyl sulfonate by 100 parts.
7. The preparation method of the halogen-free flame-retardant polyacrylonitrile fiber according to claim 1, characterized in that: the concentration of the hydrazine hydrate, guanidine or amine crosslinking agent solution in the step (3) is 10-30 wt%; the concentration of the NaOH solution is 7-15 wt%.
8. Halogen-free flame-retardant polyacrylonitrile fiber prepared by the preparation method of any one of claims 1 to 7.
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| CN114164521A (en) * | 2022-01-13 | 2022-03-11 | 天津工业大学 | Sheath-core structure flame-retardant polyacrylonitrile composite fiber and preparation method and application thereof |
| CN114437366A (en) * | 2022-01-25 | 2022-05-06 | 天津工业大学 | Intumescent flame retardant, preparation method and application thereof, flame-retardant polyacrylonitrile fiber and preparation method thereof |
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| CN1566421A (en) * | 2003-06-12 | 2005-01-19 | 中国石油化工股份有限公司 | Flameproof polyacrylonitrile fibre and method for preparing same |
| CN102560747A (en) * | 2011-12-11 | 2012-07-11 | 武汉纺织大学 | Preparation method of durable low-smoke halogen-free flame-retardant polyacrylonitrile fiber |
| CN104988724A (en) * | 2015-06-10 | 2015-10-21 | 四川大学 | Polyvinyl alcohol reinforcement modification halogen-free flame retardant polyacrylic composite fiber and preparation method thereof |
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| CN1566421A (en) * | 2003-06-12 | 2005-01-19 | 中国石油化工股份有限公司 | Flameproof polyacrylonitrile fibre and method for preparing same |
| CN102560747A (en) * | 2011-12-11 | 2012-07-11 | 武汉纺织大学 | Preparation method of durable low-smoke halogen-free flame-retardant polyacrylonitrile fiber |
| CN104988724A (en) * | 2015-06-10 | 2015-10-21 | 四川大学 | Polyvinyl alcohol reinforcement modification halogen-free flame retardant polyacrylic composite fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114164521A (en) * | 2022-01-13 | 2022-03-11 | 天津工业大学 | Sheath-core structure flame-retardant polyacrylonitrile composite fiber and preparation method and application thereof |
| CN114437366A (en) * | 2022-01-25 | 2022-05-06 | 天津工业大学 | Intumescent flame retardant, preparation method and application thereof, flame-retardant polyacrylonitrile fiber and preparation method thereof |
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