CN1566421A - Flameproof polyacrylonitrile fibre and method for preparing same - Google Patents
Flameproof polyacrylonitrile fibre and method for preparing same Download PDFInfo
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Abstract
The invention discloses a flame-proof polyacrylonitrile fiber and its manufacturing method. Said fiber comprises at least 5%-25% by polyacrylonitrile weight of APP flame retardant, or APP flame retardant treated by silane coupler or titanate coupler, furthmore, comprises pentaerythritol, bi-pentaerythritol and like polyhydric alcohol compound, which has a APP-to-polyhydric alcohol ratio ranging from 2 to 3.8 by wt/wt. The method for manufacturing said fiber includes: crossblending the flame retardant with the inorganic solvent spinning dope of polyacrylonitrile, which is obtained by one-step method or two-step method to prepare crossblending spinning dope, then spinning, washing, drafting and thermal sizing by using current technique of making acrylon with inorganic solvent spinning line. The invention applies cheap, non-poisonous and high efficient inorganic additive flame retardant APP to spin flame retardant acrylon, as a result, crossblending spinning dope with good spinnability and fiber with high flame retardancy is obtained.
Description
Invention field
The present invention relates to a kind of fire resistance fibre material---fire-retardant polyacrylonitrile fiber and manufacture method thereof, particularly contain ammonium polyphosphate flame retardant, and adopt the fire-retardant polyacrylonitrile fiber and the manufacture method thereof of inorganic solvent spinning.
Background technology
Polyacrylonitrile fibre (being commonly called as acrylic fibers) has the bulking intensity height, comfortable feel, and good heat preservation performance is easy to advantages such as dyeing, and is of many uses at aspects such as clothing, daily ornament and commercial Application.But its disadvantage is to be easy to burning, and the bigger hydrogen cyanide of when burning toxigenicity etc., therefore require its application of fire-retardant occasion to be restricted many.
The method of making at present flame-retardant acrylic fibre in the world mainly contains three kinds, i.e. finishing method, copolymerization method and blending method.Finishing method comprises fiber and fabric carried out the surface flame-retardant coating, and the chemical modification of gelatine silk and fiber being carried out strand.The surface-coated arrangement is also to be the method for modifying flame of most convenient early, but washing resistance is bad, and flame retardant effect is not durable, the degradations such as feel of fiber and fabric after the flame-proof treatment; The chemical modification of strand comprises-the crosslinked or cyclisation of the carboxylation of CN base and salinization, strand, strand grafting on ignition-proof element or group etc., these methods have increased the rear processing finishing operation of fiber, fire resistance improves not obviously maybe may cause some performance degradation, and complex process or technical conditions are had relatively high expectations.In addition, finishing method also easily causes environmental pollution.
Copolymerization method is the fire-resistant copolyesters body spinning technique then that the preparation of anti-flammability monomer copolymerizations such as acrylonitrile monemer and vinyl chloride, vinylidene chloride is contained ignition-proof elements such as halogen, phosphorus, this is the flame resistant method that present most of flame-retardant acrylic fibre product adopts, and its typical case's representative is a Vinyon N.This class flame-retardant acrylic fibre fire resistance is good, and flame retardant effect is lasting.Yet copolymerization method has the following disadvantages: compare with conventional acrylic fibers, change polymerization and spinning production technology; When adopting the inorganic solvent spinning, the anti-flammability content of monomer generally will be lower than 20wt%～25wt% in the soluble copolymer of inorganic solvent, be difficult to satisfy fire-retardant requirement, and when adopting organic solvent, though the anti-flammability content of monomer can be brought up to more than the 45wt% in the copolymer, cause that condensate is heat-resisting, light resistance and premium properties deteriorations such as fiber size stability and dyeability; The copolymer preparation is general adopts aqueous polymerization, but many anti-flammability water solubility of monomer such as ethylene halide are low, volatility is high, make polymerisation reactivity and aggregate rate on the low side, also bring certain difficulty to production operation simultaneously.
Blending method is with polyacrylonitrile and low molecule or the blend in solvent of macromolecule additive flame retardant, normally is blended into additive flame retardant in original polyacrylonitrile spinning solution, the spinning then of preparation co-blended spinning stoste.Usually, though the flame-retardant acrylic fibre flame retardant effect of blending method is inferior to copolymerization method, but it does not influence original polymerization process and spinning solution preparation, if select suitable additive flame retardant for use, spinning process condition and the more original acrylic fibers of fibrous physics mechanical performance do not have significant change yet, and technical process is simple, and is widely applicable, produces flexibly.Yet, because flame retardant agent content can not be too high in the fire-retardant acrylic fibers of blending type, thereby to select fire retardant efficiently, selection of fire retardant also will be considered its dissolubility or uniform and stable dispersiveness in spinning solution simultaneously, with the compatibility of polyacrylonitrile, retention rate in the fiber manufacture process and washing resistance etc.
Prior art adopts polyacrylonitrile and polyvinyl chloride, gathers fit co-blended spinning such as (vinyl chloride-vinylidene chloride) Halogen flame retardance poly, influence fibre property but these flame retardance polies are fit with polyacrylonitrile compatibility difference, added quantitative limitation simultaneously, also can not be made the acrylic fibers of high flame retardant in this way.
Guangdong chemical fibre (3): 1～14 (1989) has reported employing FR8 (octa-BDE), Melliand Textilberichte72 (5): 353～359 (1991) have reported (gathering) acrylate that adopts the phosphoric acid ester group, DE4005376A1 discloses the phosphate that adopts polyphenyl phenol, DE4026883A1 and the clear 57-30146 of special permission communique disclose and have adopted the poly-phosphine piperazine that contains organic group to make the method for fire retardant and polyacrylonitrile blended spinning flame-retardant acrylic fibre, but it all adopts dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) organic solvents such as (DMSO) to make spin solvent, and when adopting inorganic solvent, as sodium sulfocyanate (NaSCN) when the aqueous solution is made spin solvent, because these fire retardants are insoluble in spinning solution, can not uniform and stablely disperse, fire retardant with can stop up screen pack and spinneret orifice after spinning solution mixes, thereby cause spinning and drawing-off not to carry out smoothly, be difficult to obtain well behaved flame-retardant acrylic fibre.On the other hand, (gathering) acrylate of above-mentioned phosphoric acid ester group and the phosphate of polyphenyl phenol or do not have the commercially available prod, or comparatively expensive.
South China Science ﹠ Engineering University's journal (natural science edition) 24 (7): 121～127 (1996) has reported that with ammonium dihydrogen phosphate (ADP) and urea be the technical scheme of composite flame-retardant agent and polyacrylonitrile/sodium sulfocyanate-water spinning solution homogeneous phase blend spinning flame-retardant acrylic fibre.Yet, ammonium dihydrogen phosphate (ADP) and urea are material soluble in water, though can with the blend of spinning solution homogeneous phase, but solidify, fire retardant can seriously run off in the fiber manufacture process such as stretching, washing, can not obtain expecting the fiber of anti-flammability, and poor because of the fire retardant washing resistance, the durability of fire-retardant of gained fiber is bad.Researcher of the present invention finds that adopt this scheme when the total addition of fire retardant is the 20wt% of polyacrylonitrile, the limited oxygen index of gained acrylic fibers (LOI value) only is 21, and fire resistance improves very not obvious.
The anti-flammability acrylonitrile copolymer that GB1590619 discloses tetrabromophthalic anhydride (PHT4) and Halogen is the solvent co-blended spinning with DMF, to improve the technical scheme of fiber anti-flammability.PHT4 is dissolved in DMF, but is insoluble to inorganic solvents such as the NaSCN aqueous solution, can not uniform and stablely disperse in the inorganic solvent spinning solution, thereby this scheme is difficult to adopt the inorganic solvent spinning.Simultaneously as in this patent confirm that if PHT4 and the blend of non-anti-flaming polypropylene nitrile, then flame retarding efficiency is very low, can not obtain well behaved flame-retardant acrylic fibre.
Openly specially permit communique clear 63-59410 disclose aluminium salt such as the soluble aluminum nitrate of inorganic solvent such as the NaSCN aqueous solution in inorganic solvent with the anti-flammability acrylonitrile copolymer co-blended spinning of Halogen, to improve the technical scheme of fiber anti-flammability.But, these aluminium salt need to sneak in the slurry before the heating for dissolving in solvent at acrylonitrile copolymer, rather than directly be blended in the solution or spinning solution of polymer, and need pH value is adjusted to 6.0, best below 4.0 after, heating for dissolving is made co-blended spinning stoste again, and this and common acrylic fibers one-step method production process flow process are inconsistent, are unfavorable for production operation.Moreover the fire resistance of described aluminium salt pair anti-flammability acrylonitrile copolymer plays a driving role, and itself flame retarding efficiency is very low, when itself and non-anti-flaming polypropylene nitrile blend, then can not obtain well behaved flame-retardant acrylic fibre.
On the other hand, in the scene of fire, cigarette is to produce at first and the easiest deadly life and affect the fire fighting factor on opportunity adversely, so " fire-retardant " in the present age is with " pressing down cigarette " mentions in the same breath.During the acrylic fibers burning, no matter be to glow, or flaming combustion, all discharge a large amount of cigarettes.Present flame-retardant acrylic fibre product mainly is the Halogen product, not only produces poisonous hydrogen halide etc. during its burning, and further aggravates the formation of smog.
Journal of Applied Polymer Science 27 (9): 3369-3377 (1982) is by doing the effect of APP to polyacrylonitrile of having studied that mix with APP (APP) powder and polyacrylonitrile resin, and the result shows that APP has good fire retardation and presses down the cigarette effect polyacrylonitrile.But the document does not relate to polyacrylonitrile fibre.
APP is a kind of cheap and easy to get, non-toxic efficient, widely used inorganic additive flame retardant, but when being used to spin flame-retardant acrylic fibre, because it is insoluble in the organic solvent commonly used of polyacrylonitrile, can not finely disperse, and is difficult to adopt the organic solvent spinning; The APP good water solubility of low polymerization degree, solvable in the inorganic solvent spinning solution of common polyacrylonitrile, but in fiber manufacture process, can cause APP to run off in a large number, the anti-flammability and the durability of fire-retardant of gained fiber are poor; Though the APP of high polymerization degree has overcome the easily water-soluble shortcoming of low polymerization degree APP, but solubility is low even insoluble in the inorganic solvent spinning solution of common polyacrylonitrile, when adopting the co-blended spinning stoste of conventional method preparation inorganic solvent, the APP fine powder not only can not uniform and stablely disperse, and generate big solid particles, have a strong impact on the spinnability of co-blended spinning stoste.
Moreover at present most of in the world Acrylic Fibers Plant all adopt the spinning line of inorganic solvent such as the NaSCN aqueous solution, adopt this spinning line, fire retardant is blended into produces flame-retardant acrylic fibre in original polyacrylonitrile spinning solution, the needs of more realistic production.
Summary of the invention
The object of the present invention is to provide a kind of fire-retardant polyacrylonitrile fiber, described fiber has good physical and mechanical properties, fire resistance and durability of fire-retardant, and the amount of being fuming is few during burning, and has low production cost.
Another object of the present invention is to provide a kind of manufacture method of fire-retardant polyacrylonitrile fiber, described manufacture method is the inorganic solvent spinning solution blend with fire retardant and polyacrylonitrile, adopt the acrylic fibers manufacture method of existing inorganic solvent spinning line, technology is simple, produce flexibly, combine closely with production is actual.
To achieve these goals, the technical solution used in the present invention is, a kind of fire-retardant polyacrylonitrile fiber comprises the APP fire retardant of polyacrylonitrile amount 5wt%～25wt% at least.
The degree of polymerization of described APP fire retardant is at least 50, and particle diameter is smaller or equal to 3 μ m.Preferred degree of polymerization is at least 100, and particle diameter is smaller or equal to 1 μ m.In the co-blended spinning stoste of APP and spinning solution blend preparation, the content of APP is preferably the 10wt%～20wt% of polyacrylonitrile.
Described APP also can be the APP that handles through surface conditioning agent.Described surface conditioning agent is a kind of in γ-amine propyl-triethoxysilicane (KH550), methacryloxypropyl trimethoxy silane silane couplers such as (KH570), isopropyl three (dioctyl pyrophosphoryl oxygen base) the titanate esters titanate coupling agents such as (NDZ201).Can handle by the common processing method of inorganic particle with above-mentioned surface conditioning agent during surface treatment.Surface treatment can improve the compatibility of APP and polyacrylonitrile, improves the physical and mechanical properties and the fire resistance of gained fiber.
Fire-retardant polyacrylonitrile fiber of the present invention, also comprise a kind of polyol compound, described polyol compound is pentaerythrite (PER), bipentaerythrite (DPER) and is fit to other polyol compounds of the present invention that the amount of polyol compound is that APP/PER (or DPER) is 2～3.8 (wt/wt).The same when being used for plastics, coating etc. with APP, described polyol compound can further improve the flame retarding efficiency of APP, improves the anti-flammability of polyacrylonitrile fibre.
The amount of preferred polyol compound is that APP/PER (or DPER) is 2.5～3 (wt/wt).
The manufacture method of fire-retardant polyacrylonitrile fiber of the present invention, comprise fire retardant mixed with inorganic solvent and obtain the fire retardant slurry, again with the polyacrylonitrile spinning solution blend of adopting identical inorganic solvent, obtain the co-blended spinning stoste of required fire retardant concentration, then through the spray silk of prior art, solidify, technology such as washing, drawing-off and HEAT SETTING obtains described fiber.
The method that described fire retardant mixes with inorganic solvent is, fire retardant is at room temperature mixed with the inorganic solvent identical with the spinning solution solvent of 3～5 times of its weight, obtains the fire retardant slurry.
Polyacrylonitrile of the present invention is the common used acrylonitrile copolymer of spinning acrylic fibers, be acrylonitrile monemer and other copolymer of the unsaturated monomer of copolymerization with it, wherein other unsaturated monomers comprise the non-flame-retardant ethylene base monomer of not Halogen and phosphorus and contain halogen or/and the flame-retardant ethylene base monomer of phosphorus.These unsaturated monomers comprise acrylic acid, methacrylic acid and their ester class; Acrylamide and alkyl substituent thereof; Vinyl carboxylates such as vinylacetate, stearic acid vinyl ester; Non-anti-flammability monomers such as unsaturated sulfonic acids such as vinyl sulfonic acid, metering system sulfonic acid, acrylamido methyl propane sulfonic acid and its esters, and following anti-flammability monomer: Halogen vinyl monomers such as ethlyene dichloride, ethylene bromide, vinylidene chloride, methacrylic acid dibromo propyl ester; Phosphorous vinyl monomers such as diethyl allyl phosphate, diethyl phosphate acrylate; Halogens such as two (2-chloroethyl) vinyl phosphate, diethyl-2-bromo propenyl phosphate and phosphorus vinyl monomer etc.
Above-mentioned monomer can adopt the method polymerization of radical polymerization, obtains described acrylonitrile copolymer, and its method or polymeric articles are known for those skilled in the art.
In the described acrylonitrile copolymer, acrylonitrile monomer content is 50wt%～98wt%, preferred 65wt%～96wt%; Other non-anti-flammability content of monomer are 2wt%～50wt%, preferred 4wt%～35wt%; The anti-flammability content of monomer is 0～25wt%, preferred 0～20wt%.
Inorganic solvent of the present invention can adopt the inorganic solvent in the existing acrylic fibers spinning technology, as NaSCN, potassium rhodanide (KSCN), ammonium thiocyanate (NH
4The aqueous solution of rhodanate such as SCN); The muriatic aqueous solution such as zinc chloride, calcium chloride etc.The preferred NaSCN aqueous solution and solder(ing)acid, most preferably the NaSCN aqueous solution.
The inorganic solvent spinning solution of polyacrylonitrile of the present invention can adopt the spinning solution that has above-mentioned inorganic solvent in the acrylic fibers manufacturing technology now, both can be the spinning solution of acrylic fibers single step spining art, also can be the spinning solution of acrylic fibers two-step method spinning technique.The spinning solution of one-step method, be reaction monomers in solvent polymerization after the spinning solution that demonomerization obtains; The spinning solution of two-step method, be the reaction monomers polymerization after, polymer is dissolved again the spinning solution that obtains.
In order to improve the flame retarding efficiency of APP, the same when being used for plastics, coating etc. with it, when APP and spinning solution blend preparation co-blended spinning stoste, also can mix into pentaerythrite (PER), bipentaerythrite (DPER) or be fit to of the present invention other etc. polyol compound.In the case, APP/PER in the co-blended spinning stoste (or DPER) 2～3.8 (wt/wt) is preferably 2.5～3 (wt/wt).
Co-blended spinning stoste of the present invention is meant the inorganic solvent spinning solution of the polyacrylonitrile that usual method (one-step method or two-step method) is made and the co-blended spinning stoste of above-mentioned fire retardant mixed preparing.The preparation of co-blended spinning stoste is earlier fire retardant to be mixed with the inorganic solvent (identical with the solvent of spinning solution) of 3～5 times of its weight, obtains the fire retardant slurry, then gained slurry and a certain amount of spinning solution is mixed.At first at room temperature stirred 10 minutes～20 minutes, and under agitation slowly be warmed up to 60 ℃～70 ℃ then, and under this temperature, continue to stir 10 minutes～20 minutes.Preferably at room temperature stirred 10 minutes, and under agitation be warmed up to 40 ℃～50 ℃ with the heating rate of 2～3 ℃/min then, the heating rate with 1～2 ℃/min is warmed up to 60 ℃～70 ℃ again, and continues to stir 15 minutes under this temperature.Obtain the co-blended spinning stoste of required fire retardant concentration through deaeration.
The manufacture method of fire-retardant polyacrylonitrile fiber of the present invention, can adopt existing inorganic solvent spinning line to make the method for acrylic fibers, the co-blended spinning stoste that is about to above-mentioned gained through common spray silk, solidify, technologies such as washing, drawing-off and HEAT SETTING obtain described fiber.These methods are fully open in the prior art, for example referring to Fang Jun, Wu Guoming, Mei Qianfang etc., " the NaSCN solvent method spins the research that non-halogen is flame-retardant acrylic fibre ", South China Science ﹠ Engineering University's journal (natural science edition), 24 (7), 121～127 (1996), the positive autumn of rattan pine, three Pus, three Tianjin men; " Difficult combustion property ァ Network リ Le Fiber Victoria System makes method "; openly specially permit the clear 63-59410 of communique (1988); big former state man; three Tian Cunxiu good fortune; " fire-resistant property No Machine acidulants contains sticking thick liquid System making method "; the special permission clear 57-45763 of communique (1982), but the present invention is not limited to the method in the cited open source literature.
Fire-retardant polyacrylonitrile fiber of the present invention both can be the fiber of circular cross-section, also can be the fiber of odd-shaped cross section, and described odd-shaped cross section comprises pancake, triangle, trilobal, dumb-bell shape etc.The fiber of different cross section can obtain by the shape that changes spinneret orifice.
When making the fire-retardant polyacrylonitrile fiber according to the method described above, because APP can be with the uniform and stable dispersion of fine particle in spinning solution, polyol compound such as PER, DPER can be dissolved in the spinning solution, thereby gained co-blended spinning stoste has better spinnability; Because APP and polyol compound evenly distribute with fine particle in finished fiber, its particulate has been filled some cavity in the fiber simultaneously, thereby the gained fiber has good physical and mechanical properties; Because APP belongs to expansion type flame retardant, have higher phosphorous, nitrogen content, dehydration when it is heated, and generate the oxide and the polyphosphoric acid of ammonia, non-volatile phosphorus, polyphosphoric acid further makes the polyacrylonitrile charing, and then the phosphorus-charcoal layer covering substrates that form to expand, simultaneously the ammonia of Sheng Chenging completely cut off, the oxygen in the diluent air, the adding of polyalcohol promotes the charcoal layer to form, the TiO that the coupling agent of processing APP is heated and generates
2, SiO
2Deng the thermomechanical property that improves phosphorus-charcoal layer, thereby the gained fiber has good flame retardancy, and it is few to give birth to the cigarette amount during burning; Because APP has the high degree of polymerization, solubility is low or insoluble in water, and is also insoluble in common organic solvent, retention rate height in finished fiber, and washing resistance is good, thereby the gained fiber also has good durability of fire-retardant.
The specific embodiment
Below be specific embodiments of the invention, described embodiment is used to describe the present invention, rather than restriction the present invention.Except that elongation at break, the percentage number average among the embodiment is benchmark with weight.The method of testing of LOI is that fiber is paved into non-weaving cloth (150g/m
2) after, measure its LOI by the GB/T5454-1997 method, to characterize the fire resistance of fiber; The method of testing of fracture strength and elongation at break is GB/T14337-1993; The method of testing of fiber number is GB/T14335-1993.
Embodiment 1
Adopting the usual way preparation is the polyacrylonitrile spinning solution of solvent with the NaSCN aqueous solution.Consisting of of polyacrylonitrile: acrylonitrile 91.5%, methyl acrylate 7.0%, methylpropene sodium sulfonate 1.5%.Polyacrylonitrile concentration is 13% in the spinning solution, and NaSCN concentration is 45%.APP (degree of polymerization 200, Zhenjiang, Jiangsu star fire retardant factory) and above-mentioned NaSCN aqueous solution with polyacrylonitrile amount 15% obtain the APP slurry.Gained slurry and spinning solution are mixed, at first at room temperature stirred 10 minutes, under agitation be warmed up to 45 ℃ then with the heating rate of 2.5 ℃/min, heating rate with 1.5 ℃/min is warmed up to 65 ℃ again, and under this temperature, continue to stir 15 minutes, obtain co-blended spinning stoste through deaeration.Adopt the spinnerets of spinneret orifice footpath Φ 0.06mm, with-1 ℃, concentration is that 13% the NaSCN aqueous solution is coagulating bath, with gained co-blended spinning stoste according to a conventional method through the spray silk, solidify, washing, drawing-off and HEAT SETTING, obtain the fire-retardant polyacrylonitrile fiber.Co-blended spinning stoste good spinnability, the fiber number 2.2dtex of gained fiber, fracture strength 2.3cN/dtex, elongation at break 26%, LOI25.8, the amount of being fuming is few during the fiber burning.The gained fiber after 20 alkali cleanings (NaOH concentration 0.1mol/L, 90 ℃ of temperature are washed 2min at every turn) and 25 times washings (95 ℃ of water temperatures are washed 20min at every turn), its LOI25.3.
Comparative example 1
With embodiment 1, different is that spinning solution does not mix with fire retardant, but direct fabrics, the LOI of gained fiber is 18.4 only, the amount of being fuming increases nearly 2 times during burning.
Embodiment 2
Other are with embodiment 1, and different is that APP has carried out surface treatment with KH550 in advance.Co-blended spinning stoste good spinnability, gained fibre number 2.2dtex, fracture strength 2.5cN/dtex, elongation at break 29%, LOI26.4.
Embodiment 3
Other are with embodiment 2, and different is also to have mixed PER in the co-blended spinning stoste.The amount of PER is 40% of APP.Co-blended spinning stoste good spinnability, gained fibre number 2.3dtex, fracture strength 2.4cN/dtex, elongation at break 29%, LOI27.5, fiber when burning amount of being fuming is more non-to be reduced more than 2 times when fire-retardant.
Embodiment 4
Other are with embodiment 1, and the degree of polymerization of different is used APP is 700 (German Hoechst company), and adopt the spinnerets of spinneret orifice footpath Φ 0.1mm.Co-blended spinning stoste good spinnability, gained fibre number 7.6dtex, fracture strength 2.1cN/dtex, elongation at break 28%, LOI26.5.After the alkali cleaning and washing of gained fiber the same terms and number of times through in embodiment 1, its LOI26.2.
Embodiment 5
Other are with embodiment 4, and different is that polyacrylonitrile consists of: acrylonitrile 76.5%, methyl acrylate 9.0%; Vinylidene chloride 14.0%, methylpropene sodium sulfonate 0.5%, and the addition of APP is 10% of a polyacrylonitrile.Co-blended spinning stoste good spinnability, gained fibre number 6.4dtex, fracture strength 2.4cN/dtex, elongation at break 32%, LOI27.1, the amount of being fuming is few during the fiber burning.
Comparative example 2
With embodiment 5, different is that spinning solution does not mix with fire retardant, but direct fabrics, gained fiber LOI is 21.0 only, the amount of being fuming increases nearly 2 times during burning.
Embodiment 6
Other are with embodiment 5, and different is consisting of of polyacrylonitrile, acrylonitrile 80%, two (2-chloroethyl) vinyl phosphate 16%, methyl acrylate 4%.Co-blended spinning stoste good spinnability, gained fibre number 6.7dtex, fracture strength 2.3cN/dtex, elongation at break 30%, LOI28.0.
Comparative example 3
With embodiment 6, different is that spinning solution does not mix with fire retardant, but direct fabrics, gained fiber LOI only is 22.3.
Comparative example 4
Other are with comparative example 3, and different is consisting of of polyacrylonitrile, acrylonitrile 70%, two (2-chloroethyl) vinyl phosphate 26%, methyl acrylate 4%.The spinning solution spinnability is bad, gained fibre number 8.8dtex, fracture strength 1.5cN/dtex, elongation at break 16%, LOI25.0.
Embodiment 7
Adopting the usual way preparation is the polyacrylonitrile spinning solution of solvent with the solder(ing)acid.Consisting of of polyacrylonitrile, acrylonitrile 95.5%, methyl acrylate 4.0%, methylpropene sodium sulfonate 0.5%.Polyacrylonitrile concentration 13% in the spinning solution, zinc oxide concentration 60%.In advance after the KH570 surface treatment, same PER (amount of PER be APP 40%) mixes with above-mentioned solder(ing)acid together, obtains the fire retardant slurry with the APP (degree of polymerization 700) of polyacrylonitrile amount 17.5%.Obtained flame-retardant agent slurry and spinning solution are mixed, stirred under the room temperature 10 minutes at first again, under agitation be warmed up to 40 ℃ with the speed of 2 ℃/min then, the speed with 1 ℃/min is warmed up to 60 ℃ again, and under this temperature, continue to stir 10 minutes, obtain co-blended spinning stoste through deaeration.Adopting the spinnerets of spinneret orifice diameter Φ 0.06mm, is coagulating bath with 0 ℃, 25% solder(ing)acid, and co-blended spinning stoste is carried out spinning, washing, drawing-off and HEAT SETTING with well-established law, obtains the fire-retardant polyacrylonitrile fiber.Co-blended spinning stoste good spinnability, gained fibre number 2.9dtex, fracture strength 2.1cN/dtex, elongation at break 22%, LOI28.8.
Embodiment 8
Other are with embodiment 3, and the length-width ratio that different is adopts spinneret orifice to be shaped as dumb-bell shape, hole is 20: 1 a spinnerets.Co-blended spinning stoste good spinnability, gained fiber are pancake, fiber number 7.0dtex, cross section length-width ratio 7: 1, fracture strength 1.9cN/dtex, elongation at break 28%, LOI27.6.
Embodiment 9
Other are with embodiment 7, different is that polyacrylonitrile consists of, acrylonitrile 76.5%, methyl acrylate 9.0%, vinylidene chloride 14.0%, methylpropene sodium sulfonate 0.5%, and to adopt through the NDZ201 surface-treated degree of polymerization be 100 APP, and its content in co-blended spinning stoste is 5% of polyacrylonitrile.Co-blended spinning stoste good spinnability, gained fibre number 2.0dtex, fracture strength 2.6cN/dtex, elongation at break 35%, LOI25.3.
Embodiment 10
Other are with embodiment 7, and different is, and to adopt the degree of polymerization be 50 APP, and its content in co-blended spinning stoste is 25% of polyacrylonitrile, and the PER in the co-blended spinning stoste changes DPER into simultaneously, and it is 3.8 that the amount of DPER satisfies weight ratio APP/DPER.Co-blended spinning stoste good spinnability, gained fibre number 3.2dtex, fracture strength 1.8cN/dtex, elongation at break 19%, LOI29.5.
Embodiment 11
Other are with embodiment 1, and different is consisting of of polyacrylonitrile: acrylonitrile 98%, methyl acrylate 1%, methylpropene sodium sulfonate 1%.Co-blended spinning stoste good spinnability, gained fibre number 2.2dtex, fracture strength 2.2cN/dtex, elongation at break 23%, LOI25.2.
Embodiment 12
Other are with embodiment 1, and different is consisting of of polyacrylonitrile: acrylonitrile 50%, methyl acrylate 25%, vinylidene chloride 15%, two (2-chloroethyl) vinyl phosphate 10%.Co-blended spinning stoste spinnability is fair, gained fibre number 2.6dtex, fracture strength 1.8cN/dtex, elongation at break 20%, LOI30.0.
Claims (10)
1. a fire-retardant polyacrylonitrile fiber is characterized in that described fiber comprises the APP fire retardant of polyacrylonitrile amount 5wt%～25wt% at least.
2. a kind of fire-retardant polyacrylonitrile fiber according to claim 1, it is characterized in that described polyacrylonitrile is the copolymer of acrylonitrile monemer and other unsaturated monomers, wherein other unsaturated monomers comprise the non-flame-retardant ethylene base monomer of not Halogen and phosphorus and contain halogen or/and the flame-retardant ethylene base monomer of phosphorus, acrylonitrile monomer content is 50wt%～98wt% in the polyacrylonitrile, preferred 65wt%～96wt%; Other non-anti-flammability content of monomer 2wt%～50wt%, preferred 4wt%～35wt%; Anti-flammability content of monomer 0～25wt%, preferred 0～20wt%.
3. a kind of fire-retardant polyacrylonitrile fiber according to claim 2, it is characterized in that described other unsaturated monomers comprise the non-anti-flammability monomer of acrylic acid, methacrylic acid and their ester class, acrylamide and alkyl substituent, vinyl carboxylates, unsaturated sulfonic acid and its esters, and the anti-flammability monomer of Halogen vinyl monomer, phosphorous vinyl monomer and Halogen and phosphorus vinyl monomer; Described vinyl carboxylates comprises vinylacetate and stearic acid vinyl ester, described unsaturated sulfonic acid comprises vinyl sulfonic acid, metering system sulfonic acid and acrylamido methyl propane sulfonic acid, described Halogen vinyl monomer comprises ethlyene dichloride, ethylene bromide, vinylidene chloride and methacrylic acid dibromo propyl ester, described phosphorous vinyl monomer comprises diethyl allyl phosphate and diethyl phosphate acrylate, and described Halogen and phosphorus vinyl monomer comprise two (2-chloroethyl) vinyl phosphates and diethyl-2-bromo propenyl phosphate.
4. a kind of fire-retardant polyacrylonitrile fiber according to claim 1 is characterized in that the degree of polymerization of described APP fire retardant is at least 50, and particle diameter is smaller or equal to 3 μ m; Preferred degree of polymerization is at least 100, and particle diameter is smaller or equal to 1 μ m, and the content of APP is preferably the 10wt%～20wt% of polyacrylonitrile.
5. according to claim 1 or 4 described a kind of fire-retardant polyacrylonitrile fibers, it is characterized in that described fire retardant is surface treated fire retardant, surface conditioning agent is silane coupler or titanate coupling agent.
6. according to claim 1 or 4 described a kind of fire-retardant polyacrylonitrile fibers, it is characterized in that described fiber also comprises polyol compound, described polyol compound is selected from seasons four amylalcohol, bipentaerythrite, and the amount of polyol compound is the APP/ polyalcohol: 2～3.8 (wt/wt).
7. method of making the described fire-retardant polyacrylonitrile fiber of claim 1, it is characterized in that the inorganic solvent spinning solution blend of polyacrylonitrile that fire retardant and one-step method or two step method are made, be mixed with co-blended spinning stoste, adopt the inorganic solvent spinning line to make the method for acrylic fibers then, obtain described fiber through spinning, washing, drawing-off and heat setting process.
8. manufacture method according to claim 7 is characterized in that described inorganic solvent adopts the aqueous solution or the muriatic aqueous solution of rhodanate, and the aqueous solution of rhodanate is selected from the aqueous solution of NaSCN, potassium rhodanide, ammonium thiocyanate; The muriatic aqueous solution is selected from the aqueous solution of zinc chloride, calcium chloride; The preferred NaSCN aqueous solution and solder(ing)acid, most preferably the NaSCN aqueous solution.
9. according to right 7 or 8 described manufacture methods, the preparation that it is characterized in that described co-blended spinning stoste is earlier fire retardant at room temperature to be mixed with the inorganic solvent identical with the spinning solution solvent of 3～5 times of its weight, obtain the fire retardant slurry, then gained slurry and spinning solution are mixed, at first at room temperature stirred 10 minutes～20 minutes, under agitation slowly be warmed up to 60 ℃～70 ℃ then, and under this temperature, continue to stir 10 minutes～20 minutes, preferably at room temperature stirred 10 minutes, under agitation be warmed up to 40 ℃～50 ℃ then with the speed of 2～3 ℃/min, speed with 1～2 ℃/min is warmed up to 60 ℃～70 ℃ again, and continues to stir 15 minutes under this temperature; Obtain the co-blended spinning stoste of required fire retardant concentration through deaeration.
10. manufacture method according to claim 7 is characterized in that making by the shape that changes spinneret orifice the fire-retardant polyacrylonitrile fiber of circular cross-section, or makes the fire-retardant polyacrylonitrile fiber of odd-shaped cross section.
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