At present, the fire resistance of most of chemical fibres generally is to adopt back arrangement, blend or copolymerization process, goes to obtain among adding fire retardant to fiber solution.This conventional manufacture method exists significant disadvantages: the one, and the affiliation that adds of fire retardant influences the spinning properties and the mechanical property of fiber; The 2nd, general fire resistance fibre the time can discharge a large amount of harmful gas in burning, and produces to melt and drip, and influences environment; The 3rd, because the softening point of chemical fibre is lower, so non-refractory.Therefore, people improve one's methods in research constantly.Advanced improving one's methods is to adopt melamine and formaldehyde condensation products to prepare fire resistance fibre, for example, just described the method that is prepared fiber by melamine and formaldehyde condensation products among the German patent DE 2364091-B.This method is at a certain temperature, and the aqueous solution of condensation product is spun into silk, simultaneously transpiring moisture and solidify precondensate.This method be owing to can form cross-linked structure, thereby can overcome above-mentioned shortcoming preferably.Its spinning process that adopts has two kinds, and " dry reaction spinning process " and " centrifugal spinning method ", spinning speed are 10 to 500 meters/minute.But the solidification process of said method need continue considerable time, so need very long pipe-line system after spinneret.In addition, in order to reach higher (the highest 500 meters/minute) spinning speed, this method has been added in the MF condensation product and has been promoted to become fine polymer (for example polyvinyl alcohol).Yet, add the anti-flammability that such polymer can influence fiber and textiles thereof.To this, reported a kind of improving one's methods among the European patent EP 93965-A: adopt melamine that the N-alkyl replaces etc. as polymerization single polymerization monomer, with the precondensate of formaldehyde in, add the alkali metal salt of 1--20% (weight), preferred sodium hydrogensulfite is spun into silk with this solution in the atmosphere of heating.But the alkali metal salt that adds at high temperature decomposes easily, fiber rapid shaping at high temperature when being unfavorable for spinning, and the while also can influence the mechanical property of fiber.Among another part European patent EP 221330-A, described another kind again and improved one's methods: the melamine that replaces with hydroxy alkyl is as comonomer, makes the condensation product of itself and formaldehyde obtain modification, and it can be spun into fire resistance fibre equally.But emphasized need heat 90 minutes at hot bellows with the spun silk of centrifugal method in European patent EP 221330-A, continued then to keep 30 to 60 minutes, to improve the brute force of fiber, made spinning process or cycle very long, efficient is not high.The spinning process that described back two patents (being EP93965-A and patent EP221330-A) adopt is all identical with the spinning process that German patent (DE2364091-B) provides, promptly must be the substitution reaction of carrying out melamine earlier, and then with this monomer and formaldehyde reaction.Though improving one's methods so do not add the spinning process that polyvinyl alcohol can realize that also Deutsche Bundespatent (DE2364091-B) provides, and all increased production process, prolonged the production cycle, improved production cost.
The objective of the invention is at the deficiencies in the prior art, a kind of new fire resistance fibre and manufacture method thereof are provided, it can improve the mechanical property of fire resistance fibre, and then improve the wearability of fire resistance fibre goods, it is simple simultaneously to have production technology again, production efficiency improves, the characteristics that production cost descends.
The present invention seeks to following realization: designing a kind of is that the fire resistance fibre of main component is characterized in that this fire resistance fibre prescription is with the melamine:
The polymer of melamine and formaldehyde compound accounts for the 90--99% of fire resistance fibre weight;
Inorganic nano material accounts for fire resistance fibre weight 10--1%, wherein,
The mol ratio of melamine and formaldehyde compound is 1: 1.2--1: 6;
Described formaldehyde compound comprises formaldehyde and substance, and both account for the 85--30% and the 15--70% of formaldehyde compound mole respectively;
Described substance is at least a in the following material: ethylene glycol, propylene glycol, 1,4-butanediol, 1,3 butylene glycol, ethylenediamine, p-phenylenediamine (PPD), triethanolamine, monoethanolamine, glycine, glycollic acid, Beta-alanine and α alanine.
The present invention has designed a kind of manufacture method of producing above-mentioned fire resistance fibre that is applicable to simultaneously.It is characterized in that making prepolycondensate, after filtering, adopt centrifugal spinning method direct fabrics by described prescription; The rapid dry forming of gained fiber.Described centrifugal spinning process parameter is:
Prepolycondensate temperature: 35--100 ℃;
Prepolycondensate viscosity: 300--900 centipoise;
Pump feeding speed: 50--260 gram/minute;
The centrifugal pan linear velocity: 3000--7000 rice/minute;
Spinning temperature: 170--280 ℃.
The prescription of fire resistance fibre of the present invention and manufacture method, saved the substitution reaction operation that to carry out melamine in the prior art earlier, but adopt the direct reactive polymerics of compound such as melamine and formaldehyde, in compound, also add a certain amount of inorganic nano material, make prepolycondensate earlier, after filtering, adopt the centrifugal process spinning to make described fire resistance fibre.The prescription of fire resistance fibre of the present invention and production method both can be carried out chemical modification to the condensation polymer of melamine and formaldehyde, can utilize inorganic nano material to carry out the mixed modification of physics simultaneously again, helped improving the wearability and the mechanical property of fire resistance fibre.The inventive method adopts the method for directly prepolycondensate of melamine and formaldehyde being carried out chemical modification, improved the spinnability of prepolycondensate greatly, both avoided the spinning of interpolation polyvinyl alcohol ability, and influence the disadvantage of spinning speed, reduced again the elder generation to cyanurotriamide modified production process, promptly shortened spinning process, go back tenfold ground improved spinning speed (by existing spinning speed 10--500 rice/minute, bring up to 3000--7000 rice/minute), increased output; And do not need very long dry run, for example, though in the EP221330-A patent, also adopt the centrifugal method spinning, necessarily reach intensity in order to arrive, spun silk need heat 90 minutes at hot bellows, also to continue then to keep 30 to 60 minutes, the spinning production time that is prior art should be more than 120 minutes, and manufacture method of the present invention does not need very long dry run, and the spinning time is only used 30 minutes, shortened the spinning cycle greatly, also meaning has increased output.Simplify production technology, reduced energy consumption, reduced production cost, improved production efficiency.
The present invention is for the mechanical property that improves fire resistance fibre and improve its temperature tolerance, has also added inorganic nano material.The general particle diameter of employed in the past inorganic filler is bigger, and is relatively poor with the associativity of fibrous matrix, does the time spent when fiber is subjected to external force, is easy to generate stress and concentrates, thereby cause crackle, causes fibrous fracture.The present invention uses inorganic nano-particle to make filler, its meaning is: on the one hand, because the particle diameter size greatly descends, the surface area of particle also increases, thereby filler and the increase of matrix contact area, and the nanoparticle surface activated centre is many, also helps combining closely of particle and fibrous matrix, compatibility is relatively good, and fire resistance fibre is had double action toughness reinforcing and that strengthen simultaneously; On the other hand, because diameter of nano particles is extremely tiny, the fire resistance fibre diameter that spins is diminished, be the fineness that improves fire resistance fibre and created necessary condition, the average fineness of the inventive method obtained flame-retardant fiber or average diameter scope can reach 2--8 μ m, thereby can improve the serviceability of fire resistance fibre.
At least a as in alundum (Al, zinc oxide, calcium carbonate, titanium dioxide, carborundum, silicon nitride, magnesia, the aluminium nitride of the inorganic nano material that the present invention uses.Inorganic nano material accounts for the 1--10% of fibre weight.Making water in reaction is solvent.When using formalin, can not add water.In polycondensation reaction, the pH value of system generally is controlled at 7--9.5, preferred 7.5--9.In the polycondensation feed liquid before spinning, also will add a certain amount of curing agent, curing agent generally can be selected sulfuric acid, formic acid, acetate, ammonium chloride, aniline sulfate etc.Addition is 0.05～2.5% of a prepolycondensate weight.
The manufacture method of fire resistance fibre of the present invention is characterised in that by described prescription and adopts the direct reactive polymerics of compound such as melamine and formaldehyde, also adds a certain amount of inorganic nano material in compound.Make prepolycondensate earlier, after filtering, adopt the centrifugal process direct fabrics to make described fire resistance fibre; The technological parameter of described centrifugal process spinning is:
Prepolycondensate temperature: 35--100 ℃;
Prepolycondensate viscosity: 300--900 centipoise
Pump feeding speed: 40--260 gram/minute;
The centrifugal pan linear velocity: 3000--7000 rice/minute;
Spinning temperature: 170--280 ℃.
Described spinning technique preferred parameter is:
Prepolycondensate temperature: 40--90 ℃;
Prepolycondensate viscosity: 400--800 centipoise
Pump feeding speed: 50--200 gram/minute;
The centrifugal pan linear velocity: 4000--6000 rice/minute;
Spinning temperature: 190--270 ℃.
The inventive method is in preparation during described prepolycondensate, can be earlier with formalin with after melamine mixes, add other recipe ingredient again; But also can add all recipe ingredients simultaneously.
Below provide specific embodiments of the invention.
Embodiment 1:
Get concentration and be 73 milliliters of (1 moles of formaldehyde of formalin of 37%, 30 grams), 12.4 gram monoethanolamines (0.2 mole), 5 gram nano-aluminium oxides and 126 gram (1 mole) melamines are put into formalin, after stirring, the pH value of mixed solution is adjusted into 7, and reaction temperature is 35 ℃; When viscosity reaches 300 centipoises, behind the adding 0.07 gram acetate, stop to stir, and immediately mixed material filtering; After the filtration, enter measuring pump, enter the centrifugal box-spinning machine spinning then.Spinning technology parameter is designed to: pump is for amount 100 gram/minute; Centrifugal pan linear velocity or spinning speed are 3000 meters/minute.Feed liquid can be spun into staple fibre rapidly.Wet staple fibre in dropping process, with temperature be that hot-air in 180 ℃ the spinning manifold fully crosses, the moisture in the fiber is evaporated rapidly.After fiber was fallen receiver, dry forming stopped 25 minutes again, further behind the solid phase polycondensation, promptly made finished product fire resistance fibre of the present invention.After measured, the average diameter of the fire resistance fibre of gained is 8 μ m.
Embodiment 2:
Get concentration and be 37% 73 milliliters of formalins (1 moles of formaldehyde), put into 126 gram melamines, after stirring, again 142.6 gram ethylene glycol (2.3 moles) and 14 gram nanometer silicon carbides are put into formalin, pH value adjusts to 8, and reaction temperature is 60 ℃, when viscosity reaches 800 centipoises, after adding 5.6 gram formic acid, stop to stir, existing side by side soon, mixed material filters; After the filtration, enter measuring pump, enter centrifugal box-spinning machine then.Spinning process is identical with embodiment 1, but wherein parameter has been done adjustment, and pump is 90 gram/minute for amount; The centrifugal pan linear velocity be 5000m/minute; Spinning temperature is 210 ℃, promptly can be made into finished product fire resistance fibre of the present invention.After measured, the average diameter of the fire resistance fibre of gained is 3 μ m.
Embodiment 3:
Get concentration and be 37% 146 milliliters of formalins (2 moles of formaldehyde), put into 126 gram melamines, after stirring, again 152 gram propylene glycol (2 moles), ethylenediamine 60 grams (1 mole), glycine 75 grams (1 mole) and 26 gram nano aluminum nitrides, 20 gram nano-silicon nitrides are put into formalin, pH value adjusts to 9, and reaction temperature progressively rises to 90 ℃, when viscosity reaches 900 centipoises, after adding 7.8 gram aniline sulfates, stop to stir, existing side by side soon, mixed material filters; After the filtration, enter measuring pump, enter centrifugal box-spinning machine then.Spinning process is identical with embodiment 1, and wherein parameter adjustment is: pump is for amount 250 gram/minute; 7000 meters/minute of centrifugal pan linear velocities; 270 ℃ of spinning temperatures promptly can be made into finished product fire resistance fibre of the present invention.After measured, the average diameter of the fire resistance fibre of gained is 6 μ m.
Embodiment 4:
Get concentration and be 37% 146 milliliters of formalins (2 moles of formaldehyde), put into 126 gram melamines, after stirring, again 90 grams 1,4-butanediol (1 mole) and 108 gram p-phenylenediamine (PPD) (1 mole), 30 gram nano-calcium carbonates, 22 gram nano titanium oxides are put into formalin, pH value adjusts to 8.5, and reaction temperature progressively rises to 70 ℃; When viscosity reaches 700 centipoises, behind the adding 5 gram sulfuric acid, stop to stir, the mixed material filtration soon of existing side by side after the filtration, enters measuring pump, enters centrifugal box-spinning machine then.Spinning process is identical with embodiment 1, but wherein parameter has been done adjustment, and pump is 80 gram/minute for amount; The centrifugal pan linear velocity is 6000 meters/minute; Spinning temperature is 240 ℃, promptly can be made into finished product fire resistance fibre of the present invention.After measured, the average diameter of the fire resistance fibre of gained is 2 μ m.