CN102560747B - Preparation method of durable low-smoke halogen-free flame-retardant polyacrylonitrile fiber - Google Patents
Preparation method of durable low-smoke halogen-free flame-retardant polyacrylonitrile fiber Download PDFInfo
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Abstract
The invention relates to a preparation method of durable low-smoke halogen-free flame-retardant polyacrylonitrile fiber. The preparation method of durable low-smoke halogen-free flame-retardant polyacrylonitrile fiber is characterized by comprising the following steps: 1) blending spinning solution preparation: based on the mass parts of the polyacrylonitrile powder and the phosphorus-containing flame retardant, dissolving 65-80 parts of polyacrylonitrile powder and 20-35 parts of phosphorus-containing flame retardant into a 50-52wt% sodium thiocyanate aqueous solution, and mixing to obtain the blending spinning solution, wherein the ratio of the total mass of the polyacrylonitrile powder and the phosphorus-containing flame retardant to the mass of the 50-52wt% sodium thiocyanate aqueous solution is (10-15):100; 2) wet spinning; and 3) irradiation: irradiating primary flame-retardant polyacrylonitrile fiber in an electron beam accelerator with 0.5-5MeV or a <60>Co device to obtain thedurable low-smoke halogen-free flame-retardant polyacrylonitrile fiber, wherein the irradiation dose is 20-50kGy. The fiber prepared by using the method has good flame-retardant durability and small smoke generation property.
Description
Technical field
The invention belongs to the chemical fibre material technical field, particularly relate to a kind of preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Background technology
Polyacrylonitrile fibre is one of synthetic fiber four large kinds, and its output is only second to polyester fiber and polyamide fiber in synthetic fiber, and global output has reached 3,000,000 ton/years.Polyacrylonitrile fibre is a kind of good textile product raw material, and fiber is fast light, radioresistance, softness, warming, is described as " artificial wool ", is widely used in the fields such as garment material, tarpaulin, curtain.But the shortcoming of its maximum is inflammability, and its limited oxygen index is 17～18% only, belongs to minimum in synthetic fiber, and its use is restricted to a certain extent, so acrylic fibers is flame-retardant modified significant.External already industrialization of flame-retardant acrylic fibre estimates that world's flame-retardant acrylic fibre total output has reached 15～160,000 ton/years at present, accounts for 5% of acrylic fibers total output.
The modification of fire-retardant polyacrylonitrile fiber generally has two kinds of methods: the one, and modification by copolymerization, be about to contain the vinyl compound of ignition-proof element (such as halogen and phosphorus etc.) as comonomer, carry out copolymerization with acrylonitrile and reach the purpose of modification, the advantage of this method is to have preferably flame retardant effect and durability, shortcoming is complex process, and cost is higher; The 2nd, blending and modifying, blending method is sneaked into additive flame retardant exactly (such as Sb in spinning solution
2O
3, halophosphoric acid ester type compound, bromine-containing compound etc.), its flame retardant effect is only second to copolymerization method, but the trend that the fiber tack temperature reduces and shrinkage increases that makes is arranged.But blending method is little because of equipment investment, technical process is simple, widely applicable, produce and extensively to be adopted by producer flexibly, and become one of flame-retardant modified main method of acrylic fibers.Common fire retardant is halogen containing flame-retardant and phosphonium flame retardant mostly both at home and abroad at present.Wherein adopt halogen flame to have that addition is few, flame-retarded efficiency is high and with the advantages such as the matrix phase capacitive is good, but can produce a large amount of flue gases and poisonous, corrosive hydrogen halide during material combustion, not only hinder rescue, and corrosion instrument, equipment.
Phosphorus flame retardant has then overcome the shortcoming of halogen containing flame-retardant effectively, has fire-retardant, heat insulation, oxygen barrier function, and living cigarette amount is few, also is difficult for being formed with the advantages such as poisonous gas and corrosive gas, and the adaptation epoch are to the requirement of environmental protection.
CN 1566421A discloses after ammonium polyphosphate process silane coupler or the titanate coupling agent processing, join in the aqueous solution of NaSCN of polyacrylonitrile, adopt conventional spinning technique to carry out wet spinning, made the fire-retardant polyacrylonitrile fiber, but this contains ammonium polyphosphate fire retardant polyacrylonitrile fibre and exists the problems such as the moisture absorption, migration.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber, the durability of fire-retardant of the fiber of the method preparation is good.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber is characterized in that it comprises the steps:
1) preparation of co-blended spinning stoste: be by polyacrylonitrile powder and the shared mass fraction of phosphonium flame retardant: 65～80 parts in polyacrylonitrile powder, 20～35 parts of phosphonium flame retardants, choose polyacrylonitrile powder (industrial spinning grade polypropylene nitrile powder) and phosphonium flame retardant;
Be that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 10～15: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 50～52wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, mixed 10～20 minutes, obtain co-blended spinning stoste;
2) wet spinning: (vacuum was 133～1330Pa) in 10～20 minutes 20～70 ℃ of lower vacuum standing and defoaming with described co-blended spinning stoste, after the filtration, wet spinning process routinely carries out wet spinning, obtains nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: with described nascent fire-retardant polyacrylonitrile fiber the electron-beam accelerator of 0.5～5MeV or
60Carry out irradiation on the Co device, irradiation dose 20～50kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Described polyacrylonitrile powder (industrial spinning grade polypropylene nitrile powder) is with the high molecular polymer of acrylonitrile with other second monomers, the 3rd monomer copolymerization; Wherein the quality of acrylonitrile accounts for 85～95%; The second monomer is a kind of in methyl acrylate, methyl methacrylate, vinylacetate, the acrylamide, and the mass content of the second monomer is 3～10%; The 3rd monomer is a kind of in sodium allylsulfonate, methylpropenyl sodium sulfonate, itaconic acid, vinylpyridine, the ethylene methacrylic pyridine, and the mass content of the 3rd monomer is 2～5%.The particle diameter of polyacrylonitrile powder is 200～800 orders.
The preparation of the polyacrylonitrile powder of industrial spinning level: the present invention adopts acrylonitrile polymerization to become the polyacrylonitrile powder as the raw material of preparation durability low smoke zero halogen flame retardant polypropylene nitrile fiber, is acrylonitrile and other copolymer powder that obtains by emulsion polymerisation such as comonomers such as methyl acrylate, methylpropenyl sodium sulfonates.
The general industry spinning-grade polyacrylonitrile powder that the preferred Shanghai Petrochemical Co. Ltd. of described industrial spinning grade polypropylene nitrile powder produces, model PAN 60.
Described phosphonium flame retardant is the mixing of any one or any two or more (containing two kinds) in vinyl phosphonate, vinyl phosphonate methyl esters, vinyl phosphonic acetoacetic ester, allyl methyl orthophosphoric acid, allyl etherophosphoric acid, the three hydroxy-ethyl acrylate base phosphates, and any two above (containing two kinds) is any proportioning when mixing.
The operation that the wet spinning process of conventional polyacrylonitrile fibre comprises is: spinning, washing, drawing-off, heat setting process.
Compared with prior art, the present invention has following characteristics:
1) durability of fire-retardant is good.
The present invention is that phosphonium flame retardant and the industrial spinning grade polypropylene nitrile powder that will have the response type activity are dissolved in the sodium thiocyanate water solution that concentration is 50～52wt% in proportion, adopts the conventional spinning technique of polyacrylonitrile fibre, pass through again electron beam or
60The Co gamma-ray irradiation, so that the phosphonium flame retardant with response type is grafted on the macromolecular chain of polyacrylonitrile fibre with the form of covalent bond, can water-fastness (having good washing resistance), fire retardant can not move to fiber surface simultaneously, and namely this fiber has excellent resistance to migration and durability of fire-retardant.Thereby solve durability of fire-retardant and the fire retardant migration problem of polyacrylonitrile fibre.
2) durability low smoke zero halogen flame retardant polypropylene nitrile fiber of the present invention, phosphonium flame retardant is dissolved in sodium thiocyanate water solution with molecular level, by the polyacrylonitrile fibre spinning technique of routine, can be evenly distributed in the inside of fiber, less to the mechanical property damage of fiber.
Durability low smoke zero halogen flame retardant polypropylene nitrile fiber of the present invention, phosphonium flame retardant is dissolved in sodium thiocyanate water solution with molecular level, polyacrylonitrile fibre spinning technique by routine, can be evenly distributed in the inside of fiber, produce phosphorus, nitrogen cooperative effect with the nitrogen element in the polyacrylonitrile fibre, can further improve the fire resistance of fiber.This flame retardant molecule is dispersed in the inside of fiber uniformly, can significantly improve the fire resistance of polyacrylonitrile fibre.
Can not discharge the poisonous gases such as hydrogen halides (because of not halogen-containing) when 3) burning, low cigarette, low toxicity is Green Product.Has excellent mechanical property (fracture strength and elongation at break).The durability low smoke zero halogen flame retardant polypropylene nitrile fiber of the present invention's preparation, the wet spinning technology of the conventional polyacrylonitrile fibre of reference carries out spinning, and simple and easy to do, technical value added is high.
This durability low smoke zero halogen flame retardant polypropylene nitrile fiber can be widely used in fabric, luxurious hotel's jewelry and various special material, has significant economic benefit and social benefit.
The specific embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
The preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber, it comprises the steps:
1) preparation of co-blended spinning stoste: be by industrial spinning grade polypropylene nitrile powder and the shared mass fraction of phosphonium flame retardant: 80 parts in industrial spinning grade polypropylene nitrile powder, 20 parts of phosphonium flame retardants, choose polyacrylonitrile powder and the phosphonium flame retardant of industrial spinning level; Described phosphonium flame retardant is the vinyl phosphonate methyl esters.
The general industry spinning-grade polyacrylonitrile powder that described industrial spinning grade polypropylene nitrile powder (copolymer) is produced for Shanghai Petrochemical Co. Ltd., model PAN 60, the composition of its powder copolymer is: acrylonitrile monemer 90wt%, vinylacetate 8wt%, methylpropenyl sodium sulfonate 2wt%.
Be that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 10: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 50～52wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, adopt ZSH-A type double helix cone-type mixer (Shanghai Kairi Electromechanic Device Manufacturing Co., Ltd.'s product that opens the door greatly, lower same) mix, the rotation rotating speed is 143r/min, revolution rotating speed 2r/min, mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: with described co-blended spinning stoste in 60 ℃ of lower vacuum standing and defoaming 10 minutes (vacuum is 133Pa), after the filtration, the wet spinning process of polyacrylonitrile fibre carries out wet spinning routinely, obtains nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: place the 1.0MeV electron accelerator to transmit on the bundle frame described nascent fire-retardant polyacrylonitrile fiber, utilize the electron beam irradiation fiber, lure vinyl phosphonate methyl esters and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 20kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Method of testing (following examples are identical):
The limited oxygen index test is carried out with reference to GB/T 5454-1997 " textile combustion performance test oxygen index method ".The BS5651-1978 method is adopted in the washability test, adds household laundry powder 5g/L, and bath raio is 1: 10, and temperature 50 C is washed 30min, and then clear water rinsing, oven dry are washed 12 times continuously, are equivalent to household washing 50 times.GB/T 14337-1993 is adopted in the test of fracture strength and elongation at break.
Do the Performance Detection test according to said method, the results are shown in Table 1.
Embodiment 2:
The preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber, it comprises the steps:
1) preparation of co-blended spinning stoste: be by industrial spinning grade polypropylene nitrile powder and the shared mass fraction of phosphonium flame retardant: 70 parts in industrial spinning grade polypropylene nitrile powder, 30 parts of phosphonium flame retardants, choose polyacrylonitrile powder and the phosphonium flame retardant of industrial spinning level; Described phosphonium flame retardant is the vinyl phosphonate methyl esters.
The general industry spinning-grade polyacrylonitrile powder that described industrial spinning grade polypropylene nitrile powder (copolymer) is produced for Shanghai Petrochemical Co. Ltd., model PAN 60, the composition of its powder copolymer is: acrylonitrile monemer 90wt%, vinylacetate 8wt%, methylpropenyl sodium sulfonate 2wt%.
Be that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 12: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 50～52wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, adopt ZSH-A type double helix cone-type mixer (Shanghai Kairi Electromechanic Device Manufacturing Co., Ltd.'s product that opens the door greatly, lower same) mix, the rotation rotating speed is 143r/min, revolution rotating speed 2r/min, mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: 60 ℃ of lower vacuum standing and defoaming after 15 minutes (vacuum is 399Pa), after the filtration, wet spinning process carries out wet spinning routinely with described co-blended spinning stoste, obtains nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: place the 1.0MeV electron accelerator to transmit on the bundle frame described nascent fire-retardant polyacrylonitrile fiber, utilize the electron beam irradiation fiber, lure vinyl phosphonate methyl esters and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 30kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 1.
Embodiment 3
The preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber, it comprises the steps:
1) preparation of co-blended spinning stoste: be by industrial spinning grade polypropylene nitrile powder and the shared mass fraction of phosphonium flame retardant: 75 parts in industrial spinning grade polypropylene nitrile powder, 25 parts of phosphonium flame retardants, choose polyacrylonitrile powder and the phosphonium flame retardant of industrial spinning level; Described phosphonium flame retardant is the allyl etherophosphoric acid.
The general industry spinning-grade polyacrylonitrile powder that described industrial spinning grade polypropylene nitrile powder (copolymer) is produced for Shanghai Petrochemical Co. Ltd., model PAN 60, the composition of its powder copolymer is: acrylonitrile monemer 90wt%, vinylacetate 8wt%, methylpropenyl sodium sulfonate 2wt%.
Be that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 15: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 50～52wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, adopt ZSH-A type double helix cone-type mixer (Shanghai Kairi Electromechanic Device Manufacturing Co., Ltd.'s product that opens the door greatly, lower same) mix, the rotation rotating speed is 143r/min, revolution rotating speed 2r/min, mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: 60 ℃ of lower vacuum standing and defoaming after 15 minutes (vacuum is 1330Pa), after the filtration, wet spinning process carries out wet spinning routinely with described co-blended spinning stoste, obtains nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: place the 2.5MeV electron accelerator to transmit on the bundle frame described nascent fire-retardant polyacrylonitrile fiber, utilize the electron beam irradiation fiber, lure vinyl phosphonate methyl esters and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 40kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 1.
Embodiment 4
The preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber, it comprises the steps:
1) preparation of co-blended spinning stoste: be by industrial spinning grade polypropylene nitrile powder and the shared mass fraction of phosphonium flame retardant: 75 parts in industrial spinning grade polypropylene nitrile powder, 25 parts of phosphonium flame retardants, choose polyacrylonitrile powder and the phosphonium flame retardant of industrial spinning level; Described phosphonium flame retardant is vinyl phosphonate.
The general industry spinning-grade polyacrylonitrile powder that described industrial spinning grade polypropylene nitrile powder (copolymer) is produced for Shanghai Petrochemical Co. Ltd., model PAN 60, the composition of its powder copolymer is: acrylonitrile monemer 90wt%, vinylacetate 8wt%, methylpropenyl sodium sulfonate 2wt%.
Be that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 13: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 50～52wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, adopt ZSH-A type double helix cone-type mixer (Shanghai Kairi Electromechanic Device Manufacturing Co., Ltd.'s product that opens the door greatly, lower same) mix, the rotation rotating speed is 143r/min, revolution rotating speed 2r/min, mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: 60 ℃ of lower vacuum standing and defoaming after 15 minutes (vacuum is 133Pa), after the filtration, wet spinning process carries out wet spinning routinely with described co-blended spinning stoste, obtains nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: place the 1.0MeV electron accelerator to transmit on the bundle frame described nascent fire-retardant polyacrylonitrile fiber, utilize the electron beam irradiation fiber, lure vinyl phosphonate methyl esters and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 20kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 1.
Embodiment 5
The preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber, it comprises the steps:
1) preparation of co-blended spinning stoste: be by industrial spinning grade polypropylene nitrile powder and the shared mass fraction of phosphonium flame retardant: 70 parts in industrial spinning grade polypropylene nitrile powder, 30 parts of phosphonium flame retardants, choose polyacrylonitrile powder and the phosphonium flame retardant of industrial spinning level; Described phosphonium flame retardant is three hydroxy-ethyl acrylate base phosphates.
The general industry spinning-grade polyacrylonitrile powder that described industrial spinning grade polypropylene nitrile powder (copolymer) is produced for Shanghai Petrochemical Co. Ltd., model PAN 60, the composition of its powder copolymer is: acrylonitrile monemer 90wt%, vinylacetate 8wt%, methylpropenyl sodium sulfonate 2wt%.
Be that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 14: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 50～52wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, adopt ZSH-A type double helix cone-type mixer (Shanghai Kairi Electromechanic Device Manufacturing Co., Ltd.'s product that opens the door greatly, lower same) mix, the rotation rotating speed is 143r/min, revolution rotating speed 2r/min, mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: 30 ℃ of lower vacuum standing and defoaming after 20 minutes (vacuum is 133Pa), after the filtration, wet spinning process carries out wet spinning routinely with described co-blended spinning stoste, obtains nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: described nascent fire-retardant polyacrylonitrile fiber is placed
60On the Co irradiation devices, utilize the gamma Rays fiber, lure three hydroxy-ethyl acrylate base phosphates and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 30kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 1.
Table 1
Table 1 explanation durability of fire-retardant of the present invention good (after 30 washings, limited oxygen index is high); Smog is less, and has good washing resistance; Has excellent mechanical property (fracture strength and elongation at break).
Embodiment 6:
The preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber, it comprises the steps:
1) preparation of co-blended spinning stoste: be by industrial spinning grade polypropylene nitrile powder and the shared mass fraction of phosphonium flame retardant: 65 parts in industrial spinning grade polypropylene nitrile powder, 35 parts of phosphonium flame retardants, choose polyacrylonitrile powder and the phosphonium flame retardant of industrial spinning level; Described phosphonium flame retardant is the vinyl phosphonic acetoacetic ester.
The general industry spinning-grade polyacrylonitrile powder that described industrial spinning grade polypropylene nitrile powder (copolymer) is produced for Shanghai Petrochemical Co. Ltd., model PAN 60, the composition of its powder copolymer is: acrylonitrile monemer 90wt%, vinylacetate 8wt%, methylpropenyl sodium sulfonate 2wt%.
Be that the mass ratio of the sodium thiocyanate water solution of 51wt% is 15: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 51wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 51wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, adopt ZSH-A type double helix cone-type mixer (Shanghai Kairi Electromechanic Device Manufacturing Co., Ltd.'s product that opens the door greatly, lower same) mix, the rotation rotating speed is 143r/min, revolution rotating speed 2r/min, mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: with described co-blended spinning stoste 20 ℃ of lower vacuum standing and defoaming after 20 minutes (vacuum is 133Pa), after the filtration, the wet spinning process of polyacrylonitrile fibre carries out wet spinning routinely, obtains nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: place the 0.5MeV electron accelerator to transmit on the bundle frame described nascent fire-retardant polyacrylonitrile fiber, utilize the electron beam irradiation fiber, lure vinyl phosphonate methyl esters and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 20kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 2.
Embodiment 7:
Substantially the same manner as Example 1, difference is: place the 5MeV electron accelerator to transmit on the bundle frame described nascent fire-retardant polyacrylonitrile fiber, utilize the electron beam irradiation fiber, lure vinyl phosphonate methyl esters and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 50kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 2.
Embodiment 8:
Substantially the same manner as Example 1, difference is: described phosphonium flame retardant is the allyl methyl orthophosphoric acid.
Do the Performance Detection test, the results are shown in Table 2.
Embodiment 9:
Substantially the same manner as Example 5, difference is: 3) radiation treatment: described nascent fire-retardant polyacrylonitrile fiber is placed
60On the Co irradiation devices, utilize the gamma Rays fiber, lure three hydroxy-ethyl acrylate base phosphates and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 20kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 2.
Embodiment 10:
Substantially the same manner as Example 5, difference is: 3) radiation treatment: described nascent fire-retardant polyacrylonitrile fiber is placed
60On the Co irradiation devices, utilize the gamma Rays fiber, lure three hydroxy-ethyl acrylate base phosphates and polyacrylonitrile fibre generation graft reaction into, dosage of radiation 50kGy obtains durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
Do the Performance Detection test, the results are shown in Table 2.
Table 2
Table 2 explanation durability of fire-retardant of the present invention good (after 30 washings, limited oxygen index is high); Smog is less, and has good washing resistance; Has excellent mechanical property (fracture strength and elongation at break).
Claims (2)
1. the preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber is characterized in that it comprises the steps:
1) preparation of co-blended spinning stoste: be by polyacrylonitrile powder and the shared mass fraction of phosphonium flame retardant: 65～80 parts in polyacrylonitrile powder, 20～35 parts of phosphonium flame retardants, choose polyacrylonitrile powder and phosphonium flame retardant;
Be that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 10～15: 100 by polyacrylonitrile powder and phosphonium flame retardant total amount and concentration, choose the sodium thiocyanate water solution that concentration is 50～52wt%, for subsequent use;
Be in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, mixed 10～20 minutes, obtain co-blended spinning stoste;
Described polyacrylonitrile powder is with the high molecular polymer of acrylonitrile with other second monomers, the 3rd monomer copolymerization; Wherein the quality of acrylonitrile accounts for 85～95%; The second monomer is a kind of in methyl acrylate, methyl methacrylate, vinylacetate, the acrylamide, and the mass content of the second monomer is 3～10%; The 3rd monomer is a kind of in sodium allylsulfonate, methylpropenyl sodium sulfonate, itaconic acid, vinylpyridine, the ethylene methacrylic pyridine, and the mass content of the 3rd monomer is 2～5%;
Described phosphonium flame retardant is the mixing of any one or any two or more in vinyl phosphonate, vinyl phosphonate methyl esters, vinyl phosphonic acetoacetic ester, allyl methyl orthophosphoric acid, allyl etherophosphoric acid, the three hydroxy-ethyl acrylate base phosphates, is any proportioning during any two above mixing;
2) wet spinning: 20～70 ℃ of lower vacuum standing and defoaming 10～20 minutes, after the filtration, wet spinning process routinely carried out wet spinning with described co-blended spinning stoste, obtained nascent fire-retardant polyacrylonitrile fiber;
3) radiation treatment: with described nascent fire-retardant polyacrylonitrile fiber the electron-beam accelerator of 0.5～5MeV or
60Carry out irradiation on the Co device, irradiation dose 20～50 kGy obtain durability low smoke zero halogen flame retardant polypropylene nitrile fiber.
2. the preparation method of durability low smoke zero halogen flame retardant polypropylene nitrile fiber according to claim 1, it is characterized in that: the particle diameter of polyacrylonitrile powder is 200～800 orders.
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