CN104746168A - Flame-retardant polyamide 66 fiber and preparation method thereof - Google Patents
Flame-retardant polyamide 66 fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant polyamide 66 fiber and a preparation method thereof. The method comprises the following steps: firstly, carrying out heating reaction on hydroxymethyl phenylphosphinic acid, thionyl chloride and ether in a reaction kettle in a certain mole ratio; introducing an amino gas into the prepared chloromethyl phenylphosphinic acid in a sodium hydroxide solution to carry out ammonification reaction to prepare aminomethyl phenylphosphinic acid; carrying out polymerization reaction on the aminomethyl phenylphosphinic acid, nylon 66 salt and water in the reaction kettle, and reacting to prepare the flame-retardant nylon 66; carrying out vacuum drying on the flame-retardant nylon 66; then melting and spinning to prepare the flame-retardant nylon 66 fiber. The flame-retardant nylon 66 fiber disclosed by the invention contains 0.5-15% of flame retardant aminomethyl phenylphosphinic acid; the limit oxygen index of the flame-retardant nylon 66 fiber is 30-35; the filament number is 0.5-4.0dtex; the breaking strength is 2.5-5.0cN/tex; and the flame-retardant nylon 66 fiber disclosed by the invention is good in fire resistance; the adding amount of the flame retardant is low; the mechanical strength of the nylon 66 fiber is not affected; and the use field of the nylon 66 fiber is effectively expanded.
Description
Technical field
The invention belongs to novel flame redundant material technical field, relate to a kind of fire-retardant Nylon 66 fiber and preparation method thereof, particularly relate to and a kind of halogenating reaction is carried out respectively to hydroxymethyl phenyl phosphinic acids and aminating reaction obtains fire retardant aminomethyl phenyl phosphinic acid, then aminomethyl phenyl phosphinic acid and nylon salt and water are carried out the obtained fire-retardant Nylon 6 of polymerisation in reactor, then fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber and preparation method thereof.
Background technology
The features such as nylon fabric has absorbing sweat, lightweight, toughness is good, resilience good, antiacid alkali, are best suited for one of man-made fabric of mankind's dress.Application on clothes is also one of main application of nylon fiber.But along with the raising of people's living standard, the requirement for textiles is also more and more higher, be starved of some existing defects that can overcome textiles.The limited oxygen index of common nylon fiber only has about 24, and produces drippage in combustion, belongs to combustible material, in use very easily initiation fire.Especially at electronics field, Yin Nilong and the fire that causes is countless, causes damage comparatively large, therefore, becomes current academia and industrial quarters is paid close attention to and the problem of tackling key problems jointly to nylon flame-retardant modified.
Fire resistance fibre is a kind of fire proofing, it is a kind of fiber that current countries in the world are all attached great importance to, therefore the fire resistance fibre prepared in every way in the preparation of fire resistance fibre has commercially been sold for many years, the fire resistance fibre that China produces at present is main mainly with halogen or phosphorous particulate greatly, and it is main for preparing fire resistance fibre mainly with fiber post processing greatly, such preparation method's complex process, production cost is high, and flame retardant effect is limited, to reach required fire resistance, often need the addition increasing fire retardant, these other mechanical performances just causing fiber decline to a great extent.
Phosphinic acids salt flame retardant products density is lower, and amount of flame-retardant agent is less, in electronic apparatus industry, have good application prospect.Clariant company of Germany, Pennwalt company of the U.S. and Ticona company are all to the exploitation of hypophosphite fire retardant and should be used as a lot of research.The synthetic method of various metal phosphinate fire retardant is also found out successively.As in the invention CN 98811621.9 of Clariant company in the basic conditions, prepare the method for metal phosphinate from yellow phosphorus, alkyl halide, metal hydroxides; And CN 200410104692.0, CN 102164934 A, CN 102164930 method that A, CN 1660858 adopts the mode of radical reaction from phosphinic acids source in the patent such as A, alkene or oxyalkylene, source metal prepare metal phosphinate fire retardant.A lot of painstaking effort have also been poured into the exploitation of phosphinate flame retardant by domestic many scholars and company, and achieve a lot of achievement.As CN 101747368 A provides a kind of preparation method and application of partially alkylated phosphinic acid nonalkali metal salt; CN 101830926 A provides a kind of synthetic process of dialkyl metal phosphinate adopting radical reaction to prepare from alkyl dichloro phosphorus.
Current phosphinates based flame retardant almost all based on metal phosphinate class, and is applied in polybutylene terephthalate (PBT) and nylon 6, nylon66 fiber more, respond well.About the research of non-metal phosphinate flame retardant, at present and few.Publication number is the preparation method providing a kind of melamine hypophosphite fire retardant in CN 101570518A, and this method adopts Aqueous phase preparation from melamine and phosphinic acids.This method to be limited as raw material single, and be subject to the impact of phosphinic acids strong reducing property, melamine and phosphinic acids must be added, otherwise phosphinic acids be heated and can be oxidized to phosphoric acid in air ambient simultaneously.
Patent of invention CN 103160949 A nano flame retardant nylon66 fiber and preparation method thereof, describe a kind of nylon 66 resin, nano silicon, melamine, ammonium polyphosphate and zinc oxide are mixed after through double screw extruder granulation, carry out spinning after obtained particle mixes according to a certain percentage with nylon 66 resin again.This invention is being prepared in fire-retardant Nylon 66 fiber process, nylon 66 resin need be processed through twice plasticizing, this just makes nylon66 fiber macromolecular chain significantly be destroyed, thus cause declining to a great extent of nylon 66 resin mechanical performance, in addition, the fire retardant kind that this invention uses is many, and quantity is large, complex process, too much fire retardant also can cause the mechanical performance of nylon 66 fiber to reduce.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the object of the invention is to propose a kind of fire-retardant Nylon 66 fiber and preparation method thereof, the present invention is first by hydroxymethyl phenyl phosphinic acids, thionyl chloride and ether add thermal response in a kettle. according to certain mol proportion, chloromethyl phenyl phosphinic acids obtained after completing pass into ammonia in sodium hydroxide solution to carry out aminating reaction and obtains aminomethyl phenyl phosphinic acid, again by nylon salt, water and aminomethyl phenyl phosphinic acid are polymerized and form fire-retardant Nylon 66, again fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber.Aminomethyl phenyl phosphinic acid joins in the polymerization system of fire-retardant Nylon 66 by the present invention, make fire retardant and nylon66 fiber perfect adaptation, not only can not have a negative impact to the mechanical performance of nylon66 fiber, nylon66 fiber and nylon 66 fiber can also be made when fire retardant adds little to have good flame retardant effect.
A kind of fire-retardant Nylon 66 fiber of the present invention, described fire-retardant Nylon 66 fiber contains the fire retardant aminomethyl phenyl phosphinic acid of 0.5 ~ 15% quality; The limited oxygen index of described fire-retardant Nylon 66 fiber is 30-35, and filament number is 0.5 ~ 4.0dtex, and fracture strength is 2.5 ~ 5.0cN/tex, and the structural formula of described aminomethyl phenyl phosphinic acid is:
Aminomethyl phenyl phosphinic acid flame retardant molecule amount is little, and phosphorus content is high, good flame resistance, active high, fully can be combined, be conducive to enhancing product performance with organo-functional group.
The present invention also proposes the preparation method of fire-retardant Nylon 66 fiber as above, described aminomethyl phenyl phosphinic acid, nylon salt and water certain mass are carried out polymerisation than in reactor, the obtained fire-retardant Nylon 66 of reaction, fire-retardant Nylon 66 is carried out abundant vacuumize, then carries out melt spinning and obtain fire-retardant Nylon 66 fiber.
Technical scheme as preferential:
The preparation method of fire-retardant Nylon 66 fiber of the present invention, described fire-retardant Nylon 66 preparation method is as follows:
1) in dissolution kettle, nylon salt is used water-soluble solution under 40 ~ 80 DEG C of conditions, add aminomethyl phenyl phosphinic acid, pass in reactor under nitrogen protection;
2) react 2 ~ 4 hours under temperature 220 ~ 240 DEG C, pressure 1.5 ~ 2.0MPa, when temperature is increased to 270 DEG C, release 1 ~ 2 is little of 0.2 ~ 0.4MPa gradually, keep temperature 270 ~ 280 DEG C, pressure 0.2 ~ 0.4MPa reacts 2 ~ 4 hours, then keeps temperature to unload being depressed into-0.01 ~-0.05MPa;
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66.
The preparation method of fire-retardant Nylon 66 fiber as above, the material quality ratio of described fire-retardant Nylon 66 is:
Aminomethyl phenyl phosphinic acid 0.5 ~ 15
Nylon salt 100
Water 100.
The preparation method of fire-retardant Nylon 66 fiber as above, the synthesis step of described aminomethyl phenyl phosphinic acid is:
Hydroxymethyl phenyl phosphinic acids, thionyl chloride and ether are added thermal response in a kettle., and reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal;
Chloromethyl phenyl phosphinic acids crystal is joined in sodium hydroxide solution, passes into ammonia, again filter after reaction a period of time, and by water cleaned screening repeatedly, then after super-dry obtained aminomethyl phenyl phosphinic acid.
The preparation method of fire-retardant Nylon 66 fiber as above, the mol ratio that adds of described hydroxymethyl phenyl phosphinic acids, thionyl chloride and ether is 1:1:3 ~ 10, and the chemical equation of correlated response is
The preparation method of fire-retardant Nylon 66 fiber as above, the mol ratio that adds of described NaOH and chloromethyl phenyl phosphinic acids is 1 ~ 1.2:1, and the concentration of sodium hydroxide solution is 2 ~ 50wt%, and relevant chemical equation is
The preparation method of fire-retardant Nylon 66 fiber as above, described ether is methyl phenyl ethers anisole, diphenyl ether, Chloromethyl methyl ether, chloromethyl ether, ethyl vinyl ether, EGME or glycol dimethyl ether.Ethers boiling point is lower, is a kind of conventional low-temperature solvent.
The preparation method of fire-retardant Nylon 66 fiber as above, described in add thermal response temperature be 40 ~ 80 DEG C, the reaction time is 3 ~ 6 hours, and described cooling down to 20 ~ 30 DEG C are filtered.This reaction is temperature required low, and the time is short, can effective production control cost, and after cooling, Crystal solubility reduces and separates out, and more easily carries out lock out operation; It is 0.1 ~ 0.5MPa that described ammonia adds fashionable reaction pressure, and excess of ammonia gas can ensure carrying out completely of reaction, and under the pressure of ammonia, is conducive to the carrying out of accelerated reaction;
Described reaction a period of time refers to 1 ~ 8 hour; Described repeatedly cleaning refer to wash number be 1 ~ 10 time until described filtrate pH value reaches 6 ~ 8.The sodium hydroxide solution used in the preparation process of aminomethyl phenyl phosphinic acid is strong basicity, if it can not be cleaned from fire retardant, will make a big impact to the result of use of aminomethyl phenyl phosphinic acid;
The temperature of described drying is 50 ~ 100 DEG C, and drying time is 4 ~ 8 hours.The fire retardant of abundant drying, in use can directly add in production process, avoids moisture and introduces the negative effect caused; The qualitative filter paper that the filter paper that described filtration uses is 30 ~ 120 microns, aperture.
The preparation method of fire-retardant Nylon 66 fiber as above, described vacuum drying temperature is 90 ~ 100 DEG C, and the time is 10 ~ 48 hours.The nylon66 fiber of abundant drying, is conducive to carrying out smoothly of melt spinning, improves mechanical performance and each side quality of nylon 66 fiber.
The preparation method of fire-retardant Nylon 66 fiber as above, in described melt spinning process: fire-retardant Nylon 66 melt temperature is 240 ~ 280 DEG C, the hole count of spinnerets is 10 ~ 100, aperture is 0.1 ~ 0.8mm, spinnerets draw ratio is 2.0 ~ 4.0, heat-traction temperature is 50 ~ 170 DEG C, and traction multiple is 1.1 ~ 2.0, and winding speed is 2000 ~ 5500m/ minute.
Beneficial effect:
The preparation method of a kind of fire-retardant Nylon 66 fiber of the present invention, design is unique, and step is easy, and fire retardant addition is few, successful.
Fire retardant used in the present invention is aminomethyl phenyl phosphinic acid, is a kind of BACN, and this flame retardant molecule amount is little, and phosphorus content is high.The P elements of the phenyl in this flame retardant molecule structure, the nitrogen element in amino and fire retardant all has good flame retardant effect, by the combination of concentrated ignition-proof element, make this fire retardant that fire proofing just can be made to reach good flame retardant effect when addition is little.In addition, amino in fire retardant can react with the functional group in most of macromolecular material, thus improve compatibility and the adhesion of fire retardant and macromolecular material, macromolecular material can not only be allowed to have good anti-flammability, the mechanical performance of macromolecular material can also be improved to a certain extent.Use this fire retardant can ensure to make when addition is little nylon 66 fiber have good anti-flammability, and do not affect mechanical strength and other performances of fiber.
Fire-retardant Nylon 66 fiber of the present invention, by adding fire retardant aminomethyl phenyl phosphinic acid in the course of the polymerization process, production technology is easy, lower to equipment requirement, can production control cost significantly, enhances productivity, more can guarantee that the safety of producing is carried out.The fire-retardant Nylon 66 flame-retardant fiber of preparation is good, and colourity is good, good mechanical property, can directly be applied to the fields such as military project, Aero-Space, electronics technology and civilian weaving.By this invention, the use field of nylon 66 fiber expands further, and therefore, this invention has great practical significance.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
A kind of fire-retardant Nylon 66 fiber of the present invention, fire-retardant Nylon 66 fiber contains the fire retardant aminomethyl phenyl phosphinic acid of 0.5 ~ 15% quality; The limited oxygen index of fire-retardant Nylon 66 fiber is 30 ~ 35, and filament number is 0.5 ~ 4.0dtex, and fracture strength is 2.5 ~ 5.0cN/tex, and the structural formula of aminomethyl phenyl phosphinic acid is:
Embodiment 1
A preparation method for fire-retardant Nylon 66 fiber, first synthetic ammonia methylphenylphosphinic acid, comprise the following steps:
1) be the hydroxymethyl phenyl phosphinic acids of 1:1:3 by mol ratio, thionyl chloride and methyl phenyl ethers anisole add thermal response in a kettle., the temperature adding thermal response is 80 DEG C, reaction time is 3 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal to 20 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
2) chloromethyl phenyl phosphinic acids crystal being joined concentration is in the sodium hydroxide solution of 2wt%, the mol ratio of NaOH and chloromethyl phenyl phosphinic acids is 1:1, pass into ammonia, it is 0.1MPa that ammonia adds fashionable reaction pressure, react and again filter after 1 hour, filter the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture, and clean 1 time with water and reach 8 to filtrate pH value, at temperature is 50 DEG C, obtain aminomethyl phenyl phosphinic acid after dry 4 hours again, the structural formula of aminomethyl phenyl phosphinic acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) in dissolution kettle, nylon salt is used water-soluble solution under 40 DEG C of conditions, add aminomethyl phenyl phosphinic acid, protect at nitrogen
Protect down and pass in reactor, material quality ratio is:
Aminomethyl phenyl phosphinic acid 0.5
Nylon salt 100
Water 100;
2) react 2 hours under temperature 220 DEG C, pressure 1.72MPa, when temperature is increased to 270 DEG C, release 1 is little of 0.2MPa gradually, and keep temperature 270 DEG C, pressure 0.2MPa reacts 2 hours, then keeps temperature to unload being depressed into-0.01MPa;
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66;
Then fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber, wherein vacuum drying temperature is 90 DEG C, and the time is 10 hours; In melt spinning process: fire-retardant Nylon 66 melt temperature is 240 DEG C, the hole count of spinnerets is 10, aperture is 0.1mm, spinnerets draw ratio is 2.0, and heat-traction temperature is 50 DEG C, and traction multiple is 1.1, winding speed is 2000m/ minute, the limited oxygen index of obtained fire-retardant Nylon 66 fiber is 30, and filament number is 4.0dtex, and fracture strength is 5.0cN/tex.
Embodiment 2
A preparation method for fire-retardant Nylon 66 fiber, first synthetic ammonia methylphenylphosphinic acid, comprise the following steps:
1) be the hydroxymethyl phenyl phosphinic acids of 1:1:10 by mol ratio, thionyl chloride and diphenyl ether add thermal response in a kettle., the temperature adding thermal response is 80 DEG C, reaction time is 6 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal to 30 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
2) chloromethyl phenyl phosphinic acids crystal being joined concentration is in the sodium hydroxide solution of 50wt%, the mol ratio of NaOH and chloromethyl phenyl phosphinic acids is 1.1:1, pass into ammonia, it is 0.5MPa that ammonia adds fashionable reaction pressure, react and again filter after 8 hours, filter the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture, and clean 10 times with water and reach 7 to filtrate pH value, at temperature is 100 DEG C, obtain aminomethyl phenyl phosphinic acid after dry 8 hours again, the structural formula of aminomethyl phenyl phosphinic acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) in dissolution kettle, nylon salt is used water-soluble solution under 80 DEG C of conditions, add aminomethyl phenyl phosphinic acid, protect at nitrogen
Protect down and pass in reactor, material quality ratio is:
Aminomethyl phenyl phosphinic acid 15
Nylon salt 100
Water 100;
2) react 4 hours under temperature 240 DEG C, pressure 2.0MPa, when temperature is increased to 270 DEG C, release 2 is little of 0.4MPa gradually, and keep temperature 280 DEG C, pressure 0.4MPa reacts 4 hours, then keeps temperature to unload being depressed into-0.05MPa;
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66;
Then fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber, wherein vacuum drying temperature is 100 DEG C, and the time is 48 hours; In melt spinning process: fire-retardant Nylon 66 melt temperature is 250 DEG C, the hole count of spinnerets is 100, aperture is 0.8mm, spinnerets draw ratio is 4.0, and heat-traction temperature is 170 DEG C, and traction multiple is 2.0, winding speed is 5500m/ minute, the limited oxygen index of obtained fire-retardant Nylon 66 fiber is 35, and filament number is 0.5dtex, and fracture strength is 2.5cN/tex.
Embodiment 3
A preparation method for fire-retardant Nylon 66 fiber, first synthetic ammonia methylphenylphosphinic acid, comprise the following steps:
1) be the hydroxymethyl phenyl phosphinic acids of 1:1:5 by mol ratio, thionyl chloride and chloromethyl ether add thermal response in a kettle., the temperature adding thermal response is 50 DEG C, reaction time is 5 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal to 25 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
2) chloromethyl phenyl phosphinic acids crystal being joined concentration is in the sodium hydroxide solution of 5wt%, the mol ratio of NaOH and chloromethyl phenyl phosphinic acids is 1.2:1, pass into ammonia, it is 0.3MPa that ammonia adds fashionable reaction pressure, react and again filter after 3 hours, filter the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture, and clean 5 times with water and reach 7.5 to filtrate pH value, at temperature is 80 DEG C, obtain aminomethyl phenyl phosphinic acid after dry 6 hours again, the structural formula of aminomethyl phenyl phosphinic acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) in dissolution kettle, nylon salt is used water-soluble solution under 60 DEG C of conditions, add aminomethyl phenyl phosphinic acid, protect at nitrogen
Protect down and pass in reactor, material quality ratio is:
Aminomethyl phenyl phosphinic acid 3
Nylon salt 100
Water 100;
2) react 3 hours under temperature 230 DEG C, pressure 1.6MPa, when temperature is increased to 270 DEG C, release 1.5 is little of 0.3MPa gradually, and keep temperature 275 DEG C, pressure 0.3MPa reacts 3 hours, then keeps temperature to unload being depressed into-0.02MPa;
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66;
Then fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber, wherein vacuum drying temperature is 95 DEG C, and the time is 15 hours; In melt spinning process: fire-retardant Nylon 66 melt temperature is 280 DEG C, the hole count of spinnerets is 50, aperture is 0.7mm, spinnerets draw ratio is 3.0, heat-traction temperature is 150 DEG C, traction multiple is 1.8, and winding speed is 3000m/ minute, and the limited oxygen index of obtained fire-retardant Nylon 66 fiber is 31.
Embodiment 4
A preparation method for fire-retardant Nylon 66 fiber, first synthetic ammonia methylphenylphosphinic acid, comprise the following steps:
1) be the hydroxymethyl phenyl phosphinic acids of 1:1:8 by mol ratio, thionyl chloride and Chloromethyl methyl ether add thermal response in a kettle., the temperature adding thermal response is 50 DEG C, reaction time is 4 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal to 20 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
2) chloromethyl phenyl phosphinic acids crystal being joined concentration is in the sodium hydroxide solution of 30wt%, the mol ratio of NaOH and chloromethyl phenyl phosphinic acids is 1.2:1, pass into ammonia, it is 0.3MPa that ammonia adds fashionable reaction pressure, react and again filter after 7 hours, filter the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture, and clean 8 times until filtrate pH value reaches 6 with water, at temperature is 100 DEG C, obtain aminomethyl phenyl phosphinic acid after dry 4 hours again, the structural formula of aminomethyl phenyl phosphinic acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) in dissolution kettle, nylon salt is used water-soluble solution under 50 DEG C of conditions, add aminomethyl phenyl phosphinic acid, protect at nitrogen
Protect down and pass in reactor, material quality ratio is:
Aminomethyl phenyl phosphinic acid 5
Nylon salt 100
Water 100;
2) react 3.5 hours under temperature 225 DEG C, pressure 1.8MPa, when temperature is increased to 270 DEG C, release 1 is little of 0.3MPa gradually, and keep temperature 275 DEG C, pressure 0.3MPa reacts 2.5 hours, then keeps temperature to unload being depressed into-0.03MPa; 3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66;
Then fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber, wherein vacuum drying temperature is 95 DEG C, and the time is 25 hours; In melt spinning process: fire-retardant Nylon 66 melt temperature is 270 DEG C, the hole count of spinnerets is 55, aperture is 0.6mm, and spinnerets draw ratio is 3.0, and heat-traction temperature is 80 DEG C, traction multiple is 1.8, winding speed is 3500m/ minute, the limited oxygen index of obtained fire-retardant Nylon 66 fiber is 32, filament number is 2.5dtex, and fracture strength is 3.0cN/tex.
Embodiment 5
A preparation method for aminomethyl phenyl phosphinic acid, synthesis step is:
1) be the hydroxymethyl phenyl phosphinic acids of 1:1:6 by mol ratio, thionyl chloride and methyl phenyl ethers anisole add thermal response in a kettle., the temperature adding thermal response is 60 DEG C, reaction time is 6 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal to 20 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
2) chloromethyl phenyl phosphinic acids crystal being joined concentration is in the sodium hydroxide solution of 40wt%, the mol ratio of NaOH and chloromethyl phenyl phosphinic acids is 1:1, pass into ammonia, it is 0.5MPa that ammonia adds fashionable reaction pressure, react and again filter after 2 hours, filter the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture, and clean 3 times with water and reach 8 to filtrate pH value, at temperature is 50 DEG C, obtain aminomethyl phenyl phosphinic acid after dry 4 hours again, the structural formula of aminomethyl phenyl phosphinic acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) in dissolution kettle, nylon salt is used water-soluble solution under 55 DEG C of conditions, add aminomethyl phenyl phosphinic acid, protect at nitrogen
Protect down and pass in reactor, material quality ratio is:
Aminomethyl phenyl phosphinic acid 10
Nylon salt 100
Water 100;
2) react 3 hours under temperature 235 DEG C, pressure 1.6MPa, when temperature is increased to 270 DEG C, release 1.2 is little of 0.25MPa gradually, and keep temperature 275 DEG C, pressure 0.2MPa reacts 2 hours, then keeps temperature to unload being depressed into-0.04MPa;
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66;
Then fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber, wherein vacuum drying temperature is 96 DEG C, and the time is 45 hours; In melt spinning process: fire-retardant Nylon 66 melt temperature is 250 DEG C, the hole count of spinnerets is 60, aperture is 0.6mm, spinnerets draw ratio is 2.5, and heat-traction temperature is 60 DEG C, and traction multiple is 1.8, winding speed is 4500m/ minute, the limited oxygen index of obtained fire-retardant Nylon 66 fiber is 33, and filament number is 1.2dtex, and fracture strength is 3.0cN/tex.
Embodiment 6
A preparation method for fire-retardant Nylon 66 fiber, first synthetic ammonia methylphenylphosphinic acid, comprise the following steps:
1) be the hydroxymethyl phenyl phosphinic acids of 1:1:9 by mol ratio, thionyl chloride and glycol dimethyl ether add thermal response in a kettle., the temperature adding thermal response is 50 DEG C, reaction time is 5 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal to 26 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
2) chloromethyl phenyl phosphinic acids crystal being joined concentration is in the sodium hydroxide solution of 45wt%, the mol ratio of NaOH and chloromethyl phenyl phosphinic acids is 1.1:1, pass into ammonia, it is 0.2MPa that ammonia adds fashionable reaction pressure, react and again filter after 5 hours, filter the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture, and clean 6 times with water and reach 7.5 to filtrate pH value, at temperature is 90 DEG C, obtain aminomethyl phenyl phosphinic acid after dry 7 hours again, the structural formula of aminomethyl phenyl phosphinic acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) in dissolution kettle, nylon salt is used water-soluble solution under 70 DEG C of conditions, add aminomethyl phenyl phosphinic acid, protect at nitrogen
Protect down and pass in reactor, material quality ratio is:
Aminomethyl phenyl phosphinic acid 12
Nylon salt 100
Water 100;
2) react 4 hours under temperature 235 DEG C, pressure 1.5MPa, when temperature is increased to 270 DEG C, release 2 is little of 0.24MPa gradually, and keep temperature 270 DEG C, pressure 0.4MPa reacts 4 hours, then keeps temperature to unload being depressed into-0.02MPa;
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66;
Then fire-retardant Nylon 66 is carried out abundant vacuumize, then carry out melt spinning and obtain fire-retardant Nylon 66 fiber, wherein vacuum drying temperature is 98 DEG C, and the time is 35 hours; In melt spinning process: fire-retardant Nylon 66 melt temperature is 260 DEG C, the hole count of spinnerets is 60, aperture is 0.6mm, spinnerets draw ratio is 2.2, and heat-traction temperature is 80 DEG C, and traction multiple is 1.6, winding speed is 5000m/ minute, the limited oxygen index of obtained fire-retardant Nylon 66 fiber is 34, and filament number is 1.0dtex, and fracture strength is 3.0cN/tex.
Claims (10)
1. a fire-retardant Nylon 66 fiber, is characterized in that, described fire-retardant Nylon 66 fiber contains the fire retardant aminomethyl phenyl phosphinic acid of 0.5 ~ 15% quality; The limited oxygen index of described fire-retardant Nylon 66 fiber is 30-35, and filament number is 0.5 ~ 4.0dtex, and fracture strength is 2.5 ~ 5.0cN/tex, and the structural formula of described aminomethyl phenyl phosphinic acid is:
2. the preparation method of fire-retardant Nylon 66 fiber according to claim 1, it is characterized in that, described aminomethyl phenyl phosphinic acid, nylon salt and water certain mass are carried out polymerisation than in reactor, the obtained fire-retardant Nylon 66 of reaction, fire-retardant Nylon 66 is carried out abundant vacuumize, then carries out melt spinning and obtain fire-retardant Nylon 66 fiber.
3. the preparation method of fire-retardant Nylon 66 fiber according to claim 2, is characterized in that, described fire-retardant Nylon 66 preparation method is as follows:
1) in dissolution kettle, nylon salt is used water-soluble solution under 40 ~ 80 DEG C of conditions, add aminomethyl phenyl phosphinic acid, pass in reactor under nitrogen protection;
2) react 2 ~ 4 hours under temperature 220 ~ 240 DEG C, pressure 1.5 ~ 2.0MPa, when temperature is increased to 270 DEG C, release 1 ~ 2 is little of 0.2 ~ 0.4MPa gradually, keep temperature 270 ~ 280 DEG C, pressure 0.2 ~ 0.4MPa reacts 2 ~ 4 hours, then keeps temperature to unload being depressed into-0.01 ~-0.05MPa;
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing obtain finished product fire-retardant Nylon 66.
4. the preparation method of fire-retardant Nylon 66 fiber according to claim 3, is characterized in that, the material quality ratio of described fire-retardant Nylon 66 is:
Aminomethyl phenyl phosphinic acid 0.5 ~ 15
Nylon salt 100
Water 100.
5. the preparation method of fire-retardant Nylon 66 fiber according to claim 1 and 2, is characterized in that, the synthesis step of described aminomethyl phenyl phosphinic acid is:
Hydroxymethyl phenyl phosphinic acids, thionyl chloride and ether are added thermal response in a kettle., and reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phosphinic acids crystal;
Chloromethyl phenyl phosphinic acids crystal is joined in sodium hydroxide solution, passes into ammonia, again filter after reaction a period of time, and by water cleaned screening repeatedly, then after super-dry obtained aminomethyl phenyl phosphinic acid.
6. the preparation method of fire-retardant Nylon 66 fiber according to claim 5, is characterized in that, the mol ratio that adds of described hydroxymethyl phenyl phosphinic acids, thionyl chloride and ether is 1:1:3 ~ 10; The mol ratio of described NaOH and chloromethyl phenyl phosphinic acids crystal is 1 ~ 1.2:1, and the concentration of sodium hydroxide solution is 2 ~ 50wt%.
7. the preparation method of fire-retardant Nylon 66 fiber according to claim 5, is characterized in that, described ether is methyl phenyl ethers anisole, diphenyl ether, Chloromethyl methyl ether, chloromethyl ether, ethyl vinyl ether, EGME or glycol dimethyl ether.
8. the preparation method of fire-retardant Nylon 66 fiber according to claim 5, is characterized in that, described in add thermal response temperature be 40 ~ 80 DEG C, the reaction time is 3 ~ 6 hours, and described cooling down to 20 ~ 30 DEG C are filtered; Described ammonia adds makes reaction pressure be 0.1 ~ 0.5MPa; Described reaction a period of time refers to 1 ~ 8 hour; Described repeatedly cleaning refer to wash number be 1 ~ 10 time until described filtrate pH value reaches 6 ~ 8; The temperature of described drying is 50 ~ 100 DEG C, and drying time is 4 ~ 8 hours; The qualitative filter paper that the filter paper that described filtration uses is 30 ~ 120 microns, aperture.
9. the preparation method of fire-retardant Nylon 66 fiber according to claim 2, is characterized in that, described vacuum drying temperature is 90 ~ 100 DEG C, and the time is 10 ~ 48 hours.
10. preparation method according to claim 2, it is characterized in that, in described melt spinning process: fire-retardant Nylon 66 melt temperature is 240 ~ 280 DEG C, the hole count of spinnerets is 10 ~ 100, aperture is 0.1 ~ 0.8mm, and spinnerets draw ratio is 2.0 ~ 4.0, and heat-traction temperature is 50 ~ 170 DEG C, traction multiple is 1.1 ~ 2.0, and winding speed is 2000 ~ 5500m/ minute.
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| CN112779619A (en) * | 2021-03-26 | 2021-05-11 | 北京邦维高科特种纺织品有限责任公司 | Polyamide flame-retardant fiber and product thereof |
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