CN102560747A - 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 the durable 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 durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method.
Background technology
Polyacrylonitrile fibre is one of synthetic fiber four big kinds, and its output is only second to polyester fiber and polyamide fiber in synthetic fiber, and global output has reached 3,000,000 tons/year.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 fields such as garment material, tarpaulin, curtain.But its maximum shortcoming is an inflammability, and its limited oxygen index is merely 17～18%, and genus is minimum in synthetic fiber, and its use is restricted to a certain extent, so acrylic fibers is flame-retardant modified significant.External flame-retardant acrylic fibre industrialization already estimates that world's flame-retardant acrylic fibre total output has reached 15～160,000 tons/year 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; The vinyl compound that is about to contain ignition-proof element (like halogen and phosphorus etc.) is as comonomer; Carry out copolymerization with acrylonitrile and reach the purpose of modification; The advantage of this method is to have flame retardant effect and durability preferably, and shortcoming is a complex process, and cost is higher; The 2nd, blending and modifying, blending method is sneaked into additive flame retardant (like Sb exactly 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 advantages such as the matrix compatibility 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 advantages such as poisonous gas and corrosive gas, and the adaptation epoch are to environmental protection requirement.
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 problems such as the moisture absorption, migration.
Summary of the invention
The object of the present invention is to provide a kind of durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method, the durability of fire-retardant of the fiber of this method preparation is good.
The technical solution adopted for the present invention to solve the technical problems is: durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method 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;
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 10～15: 100, chooses the sodium thiocyanate water solution that concentration is 50～52wt%, subsequent use;
Is in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, mixes 10～20 minutes, obtains co-blended spinning stoste;
2) wet spinning: (vacuum was 133～1330Pa), after the filtration, by the wet spinning process of routine, carried out wet spinning, obtained nascent fire-retardant polyacrylonitrile fiber in 10～20 minutes 20～70 ℃ of following vacuum standing and defoaming with described co-blended spinning stoste;
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%; Second monomer is a kind of in methyl acrylate, methyl methacrylate, vinylacetate, the acrylamide, and the mass content of 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 raw material of polyacrylonitrile powder as preparation durability low smoke zero halogen flame retardant polypropylene nitrile fiber, is acrylonitrile and other copolymer powder that obtains through emulsion polymerisation like comonomers such as methyl acrylate, methylpropenyl sodium sulfonates.
The general industry spinning grade polypropylene nitrile 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 any one or any mixing that (contains two kinds) more than 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 is any proportioning when (containing two kinds) more than two kinds and 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 dissolved in the sodium thiocyanate water solution that concentration is 50～52wt% having response type active phosphonium flame retardant and industrial spinning grade polypropylene nitrile powder in proportion, the conventional spinning technique of employing polyacrylonitrile fibre, pass through again electron beam or
60The Co gamma-ray irradiation; Make phosphonium flame retardant be grafted on the macromolecular chain of polyacrylonitrile fibre with the form of covalent bond with response type; Can water-fastly wash (having good washing resistance); Fire retardant can not move to fiber surface simultaneously, and promptly this fiber has excellent resistance to migration and durability of fire-retardant.Thereby solve the 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; Through 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 through routine; Can be evenly distributed in the inside of fiber,, can further improve the fire resistance of fiber with nitrogen element generation phosphorus, the nitrogen cooperative effect in the polyacrylonitrile fibre.This flame retardant molecule is dispersed in the inside of fiber uniformly, can significantly improve the fire resistance of polyacrylonitrile fibre.
Can not discharge 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 is simple and easy to do, and 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 remarkable economic efficiency and social benefit.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
Durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method, 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 the 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 polypropylene nitrile 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%.
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 10: 100, chooses the sodium thiocyanate water solution that concentration is 50～52wt%, subsequent use;
Is 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; Mix down together), the rotation rotating speed is 143r/min, revolution rotating speed 2r/min; Mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: described co-blended spinning stoste in 60 ℃ of following vacuum standing and defoaming 10 minutes (vacuum is 133Pa), after the filtration, by the wet spinning process of conventional polyacrylonitrile fibre, is carried out wet spinning, obtain 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 50 ℃ of temperature are washed 30min, and clear water rinsing then, oven dry are washed 12 times continuously, is equivalent to family expenses 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 result sees table 1.
Embodiment 2:
Durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method, 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 the 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 polypropylene nitrile 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%.
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 12: 100, chooses the sodium thiocyanate water solution that concentration is 50～52wt%, subsequent use;
Is 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; Mix down together), the rotation rotating speed is 143r/min, revolution rotating speed 2r/min; Mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: described co-blended spinning stoste after 15 minutes (vacuum is 399Pa), after the filtration, by conventional wet spinning process, is carried out wet spinning 60 ℃ of following vacuum standing and defoaming, obtain 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 result sees table 1.
Embodiment 3
Durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method, 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 the 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 polypropylene nitrile 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%.
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 15: 100, chooses the sodium thiocyanate water solution that concentration is 50～52wt%, subsequent use;
Is 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; Mix down together), the rotation rotating speed is 143r/min, revolution rotating speed 2r/min; Mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: described co-blended spinning stoste after 15 minutes (vacuum is 1330Pa), after the filtration, by conventional wet spinning process, is carried out wet spinning 60 ℃ of following vacuum standing and defoaming, obtain 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 result sees table 1.
Embodiment 4
Durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method, 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 the polyacrylonitrile powder and the phosphonium flame retardant of industrial spinning level; Described phosphonium flame retardant is a vinyl phosphonate.
The general industry spinning grade polypropylene nitrile 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%.
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 13: 100, chooses the sodium thiocyanate water solution that concentration is 50～52wt%, subsequent use;
Is 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; Mix down together), the rotation rotating speed is 143r/min, revolution rotating speed 2r/min; Mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: described co-blended spinning stoste after 15 minutes (vacuum is 133Pa), after the filtration, by conventional wet spinning process, is carried out wet spinning 60 ℃ of following vacuum standing and defoaming, obtain 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 result sees table 1.
Embodiment 5
Durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method, 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 the 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 polypropylene nitrile 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%.
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 14: 100, chooses the sodium thiocyanate water solution that concentration is 50～52wt%, subsequent use;
Is 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; Mix down together), the rotation rotating speed is 143r/min, revolution rotating speed 2r/min; Mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: described co-blended spinning stoste after 20 minutes (vacuum is 133Pa), after the filtration, by conventional wet spinning process, is carried out wet spinning 30 ℃ of following vacuum standing and defoaming, obtain 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 bergmann's 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 result sees 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:
Durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method, 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 the 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 polypropylene nitrile 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%.
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 51wt% is 15: 100, chooses the sodium thiocyanate water solution that concentration is 51wt%, subsequent use;
Is 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; Mix down together), the rotation rotating speed is 143r/min, revolution rotating speed 2r/min; Mixing time 15 minutes obtains co-blended spinning stoste;
2) wet spinning: described co-blended spinning stoste after 20 minutes (vacuum is 133Pa), after the filtration, by the wet spinning process of conventional polyacrylonitrile fibre, is carried out wet spinning 20 ℃ of following vacuum standing and defoaming, obtain 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 result sees table 2.
Embodiment 7:
Basic identical with embodiment 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 result sees table 2.
Embodiment 8:
Basic identical with embodiment 1, difference is: described phosphonium flame retardant is the allyl methyl orthophosphoric acid.
Do the Performance Detection test, the result sees table 2.
Embodiment 9:
Basic identical with embodiment 5, difference is: 3) radiation treatment: described nascent fire-retardant polyacrylonitrile fiber is placed
60On the Co irradiation devices, utilize the gamma-rays bergmann's 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 result sees table 2.
Embodiment 10:
Basic identical with embodiment 5, difference is: 3) radiation treatment: described nascent fire-retardant polyacrylonitrile fiber is placed
60On the Co irradiation devices, utilize the gamma-rays bergmann's 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 result sees 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 (5)
1. durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method 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;
By polyacrylonitrile powder and phosphonium flame retardant total amount and concentration is that the mass ratio of the sodium thiocyanate water solution of 50～52wt% is 10～15: 100, chooses the sodium thiocyanate water solution that concentration is 50～52wt%, subsequent use;
Is in the sodium thiocyanate water solution of 50～52wt% with phosphonium flame retardant and polyacrylonitrile powder dissolution in concentration, mixes 10～20 minutes, obtains co-blended spinning stoste;
2) wet spinning: described co-blended spinning stoste 20～70 ℃ of following vacuum standing and defoaming 10～20 minutes, after the filtration, by the wet spinning process of routine, is carried out wet spinning, obtain 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.
2. durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method according to claim 1 is characterized in that: 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%; Second monomer is a kind of in methyl acrylate, methyl methacrylate, vinylacetate, the acrylamide, and the mass content of 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%.
3. durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method according to claim 1 and 2, it is characterized in that: the particle diameter of polyacrylonitrile powder is 200～800 orders.
4. durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method according to claim 1 and 2; It is characterized in that: described industrial spinning grade polypropylene nitrile powder is the general industry spinning grade polypropylene nitrile powder that Shanghai Petrochemical Co. Ltd. produces, and model PAN 60.
5. durability low smoke zero halogen flame retardant polypropylene nitrile fiber preparation method according to claim 1; It is characterized in that: described phosphonium flame retardant is any one or any mixing more than 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 is any proportioning when mixing more than two kinds.
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| CN112708009A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Flame-retardant polyacrylonitrile containing methyl phosphate, and preparation method and application thereof |
| CN112746347A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of halogen-free flame-retardant polyacrylonitrile fiber |
| CN112779618A (en) * | 2020-12-31 | 2021-05-11 | 肇庆市高要区长河毛纺有限公司 | High-color-fastness spinning acrylic yarn and production process thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980419B (en) * | 2014-05-05 | 2016-07-13 | 东华大学 | A kind of halogen-free phosphorus-free inflaming retarding polyacrylonitrile complex and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578978A (en) * | 1991-09-17 | 1993-03-30 | Unitika Ltd | Production of fusion proofing and flame retardant polyester fiber |
| CN1455034A (en) * | 2002-04-29 | 2003-11-12 | 中国石油化工股份有限公司 | Fire resistant acrylonitrile copolymer fiber and manufacturing method thereof |
| 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 |
| KR20100052657A (en) * | 2008-11-11 | 2010-05-20 | 금오공과대학교 산학협력단 | Flame-retardant finish of fabrics using uv-curable phosphorous-containing monomers |
| CN102146596A (en) * | 2011-05-11 | 2011-08-10 | 四川大学 | Preparation method for halogen-free flame-retardant polypropylene fibers |
| CN102174718A (en) * | 2011-01-21 | 2011-09-07 | 武汉纺织大学 | Method for preparing anti-dripping polyester fibers |
-
2011
- 2011-12-11 CN CN 201110409365 patent/CN102560747B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578978A (en) * | 1991-09-17 | 1993-03-30 | Unitika Ltd | Production of fusion proofing and flame retardant polyester fiber |
| CN1455034A (en) * | 2002-04-29 | 2003-11-12 | 中国石油化工股份有限公司 | Fire resistant acrylonitrile copolymer fiber and manufacturing method thereof |
| 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 |
| KR20100052657A (en) * | 2008-11-11 | 2010-05-20 | 금오공과대학교 산학협력단 | Flame-retardant finish of fabrics using uv-curable phosphorous-containing monomers |
| CN102174718A (en) * | 2011-01-21 | 2011-09-07 | 武汉纺织大学 | Method for preparing anti-dripping polyester fibers |
| CN102146596A (en) * | 2011-05-11 | 2011-08-10 | 四川大学 | Preparation method for halogen-free flame-retardant polypropylene fibers |
Non-Patent Citations (1)
| Title |
|---|
| 刘伟 等: "辐照接枝阻燃涤纶纤维的开发", 《中国核科学技术进展报告-中国核学会2009年学术年会论文集（第5册）》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936760A (en) * | 2012-11-05 | 2013-02-20 | 歌山建设集团有限公司 | Flame retardant polyacrylonitrile fiber and preparation method thereof |
| CN102936760B (en) * | 2012-11-05 | 2015-04-22 | 歌山建设集团有限公司 | Flame retardant polyacrylonitrile fiber and preparation method thereof |
| CN103484966A (en) * | 2013-08-15 | 2014-01-01 | 苏州龙杰特种纤维股份有限公司 | Polyacrylonitrile fiber with flame resistance and preparation method thereof |
| CN103451912A (en) * | 2013-09-03 | 2013-12-18 | 际华三五零九纺织有限公司 | Durable flame retardant after finishing method of fabric by virtue of electron beam irradiation |
| CN103451912B (en) * | 2013-09-03 | 2015-12-23 | 际华三五零九纺织有限公司 | Utilize electron beam irradiation to the durable flame-proof afterfinish method of fabric |
| CN105316801A (en) * | 2014-07-22 | 2016-02-10 | 句容市润龙纺织品有限公司 | Preparing method for flame-retardant anti-dripping functional fibers |
| CN109457473A (en) * | 2018-10-18 | 2019-03-12 | 江苏华东纺织产品检测有限公司 | A kind of grafting method for modifying flame of wool fabric |
| CN109537099A (en) * | 2018-12-04 | 2019-03-29 | 宿迁广和新材料有限公司 | A kind of multicomponent polymeric blending fire retardant precursor and preparation method thereof |
| CN112708009A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Flame-retardant polyacrylonitrile containing methyl phosphate, and preparation method and application thereof |
| CN112746347A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of halogen-free flame-retardant polyacrylonitrile fiber |
| CN112779618A (en) * | 2020-12-31 | 2021-05-11 | 肇庆市高要区长河毛纺有限公司 | High-color-fastness spinning acrylic yarn and production process thereof |
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