CN106884217A - Nylon fiber and preparation method thereof - Google Patents

Abstract

The present invention discloses a kind of preparation method of nylon fiber, including directly carries out spinning after carrying out polymerisation comprising the raw material of 1,5 pentanediamine and adipic acid.Pass through nylon fiber obtained in preceding method present invention also offers one kind.The method of the present invention is prepared for nylon 56 using nylon polymerization by the way of the straight spinning of melting is combined, and reduces production cost, reduces waste gas discharge and the pollution to environment.High performance nylon fiber prepared by the present invention, can be further used for being made the textile materials such as yarn, woven fabric, looped fabric or non-woven fabrics, the fields such as dress material clothes, industry, decorative carpet can be applied to, with wide prospects for commercial application.

Description

Nylon fiber and preparation method thereof

The application is divisional application, and the Application No. 201310522015.X of its parent application, the applying date is 2013 10 The moon 28, entitled " nylon fiber and preparation method thereof ".

Technical field

The present invention relates to a kind of nylon fiber and preparation method thereof, specially fiber of nylon 56 and preparation method thereof.

Background technology

Nylon fiber is one of synthetic fibers of input industrialized production earliest in the world, and yield occupies the in synthetic fibers Two.Low denier silk (200~700dtex) of nylon has fracture strength high, wear-resisting, endurance, impact resistance, good stability of the dimension etc. Feature, is widely used in war products, rubber framework material, air bag silk and rope, net, rope class, tarpaulin, industrial filter cloth etc. Field；Simultaneously because its is soft, texture is slim and graceful, drapability is good, ventilative moisture absorption, elasticity are good, easy to process etc. good takes Property, possess good market prospects in fields such as high-grade sewing thread silk, T-shirt silk, umbrella fabric, motion textiles.

Wherein, nylon 6 (PA6) and nylon 66 fiber occupy the market share of nylon fiber more than 90%.However, both All there is itself in polymerization and spinning process, cause economic benefit to decline.For PA6, due to the melt after its polymerization In there is more unreacted monomer, therefore melt direct fabrics after polymerization cannot be realized, the melt after polymerization must through cooling, Wash unreacted monomer after pelletizing with water, re-dry, melting can just carry out spinning, so cause mass energy waste and Pollution to environment.For PA66, because its crystallization rate is too fast, cause spinnability poor, especially when fine denier filament is spinned, its Even dyeing rate is more difficult to control, while the reason for the high-melting-point and its configuration aspects of PA66, causing in spinning process easily There is crosslinking phenomena, the presence of problem above causes that the cost of spinning of PA66 is higher by more than 10,000 yuan/ton compared with PA6.

Additionally, current nylon is essentially all to be obtained as raw material using the derivative of oil, for example market share amount is most Big nylon 6 and nylon66 fiber, their raw material caprolactam and adipic acid are reoxidized by hydrogenation by benzene class homologue Series reaction is obtained, and hexamethylene diamine is prepared by catalytic hydrogenation method again by butadiene or acrylonitrile elder generation Adiponitrile, Whole synthesis technique is complicated, and there is certain pollution.

For a long time, people are waited in expectation and use the renewable plant resources grown by the absorbing carbon dioxide from air The green nylon suitable with existing kind properties of nylons is prepared as parent material, the dependence to non-renewable energy is solved, built Make Circular Society Construction.In this context, for 1, the 5- pentanediamines that are obtained by lysine decarboxylation as obtained in raw material Nylon, especially nylon 56 (PA56), it makes us expecting very much as the polymer of plant origin.

Polymerization for PA56 at present and be still in the junior stage using research and development, due to raw material limitation relevant report very It is few.Recorded in non-patent literature 1 (J.Polym.Sci.2,306,1947) by heating the nylon 56 that condensation methods are made.So And, it passes through with non-patent literature 2 (J.Polym.Sci.2,306,1947), non-patent literature 3 (CN200980118941.2) Nylon 56 is compared obtained in interface polycondensation, and fusing point is low and heat resistance is deteriorated.But, interface polycondensation operation is extremely complex, difficult To be industrially applicable.

Patent document 1 (CN201310049401.1), patent document 2 (CN201310074772.5) pass through process optimization system Obtained the nylon 56 with application value.Patent document 3 (CN200980118941.2) can be used for by boiling water treating PA56 of air bag is prepared, the preparation method not only increases production process, while high, narrowly distributing to obtain molecular weight Nylon 56, employs the mode that phase-polymerization is reinforced in pre-polymerization so that whole process cycle is long, high energy consumption.

The content of the invention

For the deficiency that above-mentioned existing nylon fiber and technology of preparing are present, it is an object of the invention to provide one kind using poly- After conjunction melt direct spinning come prepare the fiber of nylon 56 method and by the method prepare suitable for different application field The fiber of nylon 56 of performance requirement.

Another object of the present invention is to provide a kind of manufactured goods comprising the fiber of above-mentioned nylon 56.

A kind of preparation method of nylon fiber, wherein, will carry out being polymerized instead comprising the raw material of 1,5- pentanediamines and adipic acid Spinning is directly carried out after answering.

According to an embodiment of the present invention, the polymerisation comprises the following steps：1) by 1,5- pentanediamines and oneself two Acid is made into nylon saline solution；2) the nylon saline solution is concentrated；3) by the nylon saline solution precondensation after concentration, obtain Prepolymer；4) by the further dehydration polymerization of the prepolymer, the melt of nylon 56 is obtained.

Another implementation method of the invention, the spinning includes：A) melt after polymerisation is sprayed through spinneret Go out, form melt stream；B) melt stream solidifies out into strand through blowing；C) tow collecting machine is oiled；D) by institute State strand and obtain nylon fiber through drawing-off and post-processing.

Another implementation method of the invention, the step 1) nylon saline solution in the mass fraction of nylon salt be 55%~80%.

Another implementation method of the invention, the step 1) pH value of nylon saline solution when being diluted to 10% be 7~9.

Another implementation method of the invention, also including adding other comonomers and/or additive the step of, it is described Additive is selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, pigment, gloss enhancer, dyestuff, crystal nucleating agent, delustering agent, increasing One or more in modeling agent, antistatic additive, fire retardant, metal and slaine.

Another implementation method of the invention, described other comonomers be selected from amino acid, lactams, aromatics, aliphatic series, Alicyclic dicarboxylic acid, aromatics, aliphatic series, alicyclic diol, aromatics, aliphatic series, alicyclic diamine, aromatics, aliphatic series, cycloaliphatic hydroxyl group carboxylic One or more in acid, and above-mentioned monomer derived thing.

Another implementation method of the invention, the temperature of the concentration step is 80 DEG C~150 DEG C, pressure be 0.01 to 0.5MPa。

Another implementation method of the invention, the nylon saline solution is concentrated into the mass fraction of the nylon salt It is 70%~95%.

Another implementation method of the invention, the nylon saline solution is concentrated into the mass fraction of the nylon salt It is 80%~90%.

Another implementation method of the invention, the pressure of the precondensation steps is 0.5~2.2MPa.

Another implementation method of the invention, the pressure of the precondensation steps is further 0.8~1.7MPa.

Another implementation method of the invention, the dehydration polymerization step includes flash distillation, and the flash temperature is 260 DEG C ~320 DEG C.

Another implementation method of the invention, the temperature of the dehydration polymerization is 250 DEG C~290 DEG C, pressure be 0 to- 0.09MPa。

Present invention also offers a kind of nylon fiber prepared according to the above method.

Another implementation method of the invention, adipyl pentanediamine construction unit accounts for the nylon fiber repeat unit At least 50%.

Another implementation method of the invention, the nylon fiber is included by 1,5- pentanediamines, adipic acid and other lists Body copolymerization formed copolymer, described other monomers be selected from amino acid, lactams, aromatics, aliphatic series, alicyclic dicarboxylic acid, aromatics, Aliphatic series, alicyclic diol, aromatics, aliphatic series, alicyclic diamine, aromatics, aliphatic series, cycloaliphatic hydroxyl group carboxylic acid, and above-mentioned monomer spread out One or more in biology.

Invention further provides a kind of nylon fiber product, comprising above-mentioned nylon fiber.

The present invention is prepared for nylon 56 using nylon polymerization by the way of the straight spinning of melting is combined, and uses the low pH of high concentration The nylon saline solution of value, while using low temperature, the process conditions of low pressure, so as to reduce production cost, reducing the discharge of waste gas And the pollution to environment.

Straight spinning is melted after polymerization and eliminates the processes such as cooling, granulation, drying, melting, cost is significantly reduced, while the work Skill overcome nylon 56 through cool down repeatedly, heat melting, at high temperature the residence time it is long caused by molecular weight distribution broaden, with And fine hair and the problem of fracture of wire for being uniformly directed strand and triggering are difficult in spinning and drawing process.

The present invention has also been obtained by technique adjustment must coordinate solid phase just getable high score by being polymerized in the past Son amount, the melt of nylon 56 of Narrow Molecular Weight Distribution, control the stability of spinning melt, melt spinnability are improve, to obtain The fiber of nylon 56 of function admirable is laid a good foundation.

Using the method for the invention can according to application field and performance requirement it is different by change technological parameter come The fiber number and intensity of the fiber of nylon 56 are adjusted, operating process is simple, convenient.The nylon 56 obtained using the method for the invention is fine Dimension can be used with more traditional polyamide fibre limited oxygen index (29~35%) high as fire proofing.

Have using the fiber of nylon 56 of the method for the invention preparation and absorbed water faster and drainage rates compared with conventional nylon, Water absorption rate can adjust crystallinity and be adjusted with the degree of orientation by spinning technique, and maximum up to 12-14%, (conventional nylon fiber is maximum Hydroscopicity be 8~10%), be closest to a kind of popular chemical fiber of natural fiber.The performance makes it possess in garment industry Vast potential for future development.

The fiber of nylon 56 manufactured by the method according to the invention has excellent tensile strength (3~12cN/dtex), because This in addition to it can be further used for being made yarn, woven fabric, looped fabric, non-woven fabrics and carpet etc. for civilian fiber art, The industrial fiber field higher to intensity requirement such as tire cord, conveyer belt can also be applied to.Nylon of the invention 56 Environment-friendly materials are belonging to, its raw material sources solves the dependence to non-renewable energy in reproducible plant, are circulated beneficial to building Type society.

Brief description of the drawings

Fig. 1 is the process flow diagram of nylon fiber preparation method of the invention.

Wherein, description of reference numerals is as follows：

1st, into salt oven 2, pans 3, the first preheater

4th, thickener 5, the second preheater 6, reactor；

7th, additive tank 8, flash vessel 9, pre-polymerization device

10th, post polymerizer 11, spinning manifold 12, cross air blowing device

13rd, spinning shaft 14, oiling device 15, the first godet

16th, the second godet 17, winch spool.

Specific embodiment

After polymerization melt direct spinning have low energy consumption, low cost, pollution less, fiber quality stabilization etc. many merits, so And some polymer properties or technical problem cause part macromolecule directly cannot spin to obtain fiber by melting after polymerization, the present invention The technique still belongs to the first for nylon 56.

The present inventor conducts in-depth research to the continuous polymerization of nylon 56, spinning technique, by controlling nylon salt water-soluble The concentration and pH value of liquid, polymerization temperature, polymerization pressure, polymerization vacuum, filament spinning component pressure, condition of spinning manifold temperature, cross air blasting Speed and stability, finish and oiling device be obtained molecular weight distribution 1.2~3,0.1~10dtex of fiber number, intensity 3~ The fiber of green nylon 56 of 12cN/dtex.

Polymerization and spinning process adjust the generation for effectively inhibiting crosslinking by pH value and polymerization temperature.Continuous and stable Polymerization technique ensure that the narrow ditribution of the molecular melt amount of nylon 56 distribution.By improving nylon salinity, reducing polymerization temperature Heating energy consumption is effectively reduced with polymerization pressure.1,5- pentanediamines are reduced by the pH value and polymerization pressure that adjust nylon salt Discharge of steam, reduce pollution.The molecular weight of nylon 56 is adjusted by catalyst, salting liquid pH value and polymerization, spinning technique, The indirect control intensity of nylon 56.

Dyeing uniformity is obtained by side-blown wind velocity and stability, condition of spinning manifold temperature, component pressure and finish excellent The fine denier filament of nylon 56.Herein described method overcomes straight spinning after the monomer residue of traditional commerce nylon 6 cannot be realized being polymerized Problem, overcome nylon66 fiber spinnability it is poor, easily crosslinking, easily there is uneven dyeing problem in fine denier filament, is one in nylon fiber field Important breakthrough, while the fiber of nylon 56 as obtained in method provided by the present invention has referring to higher than the limit oxygen of conventional nylon fiber Number and saturation hydroscopicity.

The preparation method of nylon fiber of the invention, including will be comprising straight after the polymerizable raw material of 1,5- pentanediamines and adipic acid Tap into row spinning.

Nylon polymerization technique realizes that industrialized method mainly has two kinds, and one kind is continuous polymerization technique, and one kind is interval Formula polymerization technique, two kinds of technological principles are identical, and its difference essentially consists in technological process and product application range.The present invention In, the implementation to 1,5- pentanediamines and the polymerisation of adipic acid is not limited, can be by appointing in above two technique One kind is realized.

In the preparation method of nylon fiber of the invention, the polymerisation further includes following steps：1) by 1,5- Pentanediamine and adipic acid are made into nylon saline solution；2) the nylon saline solution is concentrated；3) by the nylon salt solution after concentration Solution precondensation, obtains prepolymer；4) by the further dehydration polymerization of the prepolymer, the melt of nylon 56 is obtained.

In the preparation method of nylon fiber of the invention, the spinning process is further included：A) by after polymerisation Melt sprays through spinneret, forms melt stream；B) melt stream solidifies out into strand through blowing；C) by the strand collection Beam oils；D) strand is obtained into nylon fiber through drawing-off and post-processing.

Device for preparing nylon fiber of the invention, including for the reaction member that polymerisation occurs, Yi Jiyu The electrospinning unit that the reaction member is connected, wherein, reaction member include being sequentially communicated into salt oven, pans, first pre- Hot device, thickener, the second preheater, reactor, flash vessel, pre-polymerization device and post polymerizer, electrospinning unit include spinning manifold (built-in melt distribution pipe, measuring pump, filament spinning component), cross air blowing device, spinning shaft, oiling device, the first godet, second Godet and winch spool.Wherein, reaction member can also further include additive tank.

Device for preparing nylon fiber of the invention, further, reaction member may also include additive tank, and this adds Plus agent groove is connected with reactor, flash vessel.

Device for preparing nylon fiber of the invention, further, according to actual needs, electrospinning unit may also include Three, the 4th godets.

The idiographic flow of the preparation method of nylon fiber of the invention is：By 1,5- pentanediamines and adipic acid in into salt oven Nylon saline solution is made into, pans are then transferred to, after nylon salting liquid is preheated with certain flow rate through the first preheater, entered Thickener, salting liquid enters reactor after being concentrated into prescribed concentration after the preheating of the second preheater, through high temperature, height in reactor After pressure pre-polymerization, required additive is injected by additive tank, then solution enters the remaining most of moisture of flash steam removing, finally Sequentially pass through forward and backward polymerizer and obtain the melt of nylon 56, after melt is driven into spinning manifold using gear pump, sprayed by spinneret Go out, cooled down in spinning shaft through cold wind blower, oiled after boundling, through deflector roll drawing-off, sizing, it is lax after be wound into fibre Dimension.

1,5- pentanediamines source of the invention does not limit, and can be prepared by chemical method, or using biological legal system Standby.Those skilled in the art can know, by lysine (salt) lysine decarboxylase (EC 4.1.1.18) effect Under, two end carboxyls are sloughed, pentanediamine can be generated.For example " 1B decarboxylation enzymatic property and application study " (Jiang Lili, Nanjing is big Learn, Master's thesis) in disclose specific bioanalysis and prepare pentanediamine method.For example " microorganism conversion 1B is corpse again Specific bioanalysis is disclosed in the research of amine " (Zhu Jing, University Of Science and Technology Of Tianjin, Master's thesis, 2009.3) prepare pentanediamine Method.

In the preparation method of nylon fiber of the invention, step 1) the concentration of nylon saline solution be preferably mass fraction It is 55%~80% aqueous solution, the mass fraction refers to the quality of nylon salt and the ratio of nylon saline solution quality.1, 5- pentanediamines it is highly hydrophilic, can cause its with water evaporation gasify, and polymerisation generation before, as far as possible ensure highly concentrated The nylon saline solution of degree, to suppress acid, amine proportional imbalance caused by the volatilization by 1,5- pentanediamines, meanwhile, reduce 1,5- penta 2 The volatilization of amine can also reduce pollution, reduce energy consumption.

Will not be with temperature as the solubility of the 1,6- hexamethylene diamines of the raw material of common nylon 66 and the salt of adipic acid in water Rising and significantly increase, if the salinity is too high, can occur crystallization for sediment problem, thus must be by the aqueous solution Salinity regulation be of about 50% weight, but if the temperature of the aqueous solution is low, though concentration be 50% weight or lower, Can recrystallize.Therefore, it had been thought that being technically difficult to improve the salinity of the aqueous solution in raw material preparation process.Phase Instead, we have found that, it is very high as the solubility of 1, the 5- pentanediamines of the raw material of nylon 56 and the salt of adipic acid in water, and can Continue to improve with the further increase of temperature.But because too high temperature easily makes nylon salt aoxidize or decompose again, therefore, nylon The concentration of saline solution is more preferably 60%~80%.

In the preparation method of nylon fiber of the invention, step 1) nylon saline solution in pentanediamine and adipic acid ratio 0.95~1.05 (mol ratio) is ranged preferably from, the pH value of nylon saline solution is preferably 7~9, because nylon polymerization reaction is carboxylic Base is dehydrated the process to form acid amides with amino, if binary acid and diamine equimolar theoretically, after all of monomer reaction A super high molecular weight polymer for strand can be formed.On the one hand, the molecular weight of nylon product need to be controlled, if molecule The too high then not easy processing of amount, on the other hand, because the effumability of 1,5- pentanediamines causes it with adipic acid in polymerization process Proportional imbalance, so that the molecular weight reduction of the polymer for being generated, and pH value exactly reflects binary acid and diamine ratio Parameter.Therefore, the pH value of nylon saline solution of the invention is more preferably 7.2~8.2.

For ease of the comparing with sample parameters, the pH value of nylon saline solution of the invention is with water that nylon salt is water-soluble Liquid is diluted to value measured when 10%.

In the preparation method of nylon fiber of the invention, step 1) nylon saline solution in can as needed add and be less than Antioxidant of the 1000ppm relative to nylon salt weight.Described antioxidant can be hindered phenol series compound, hydroquinones system Compound, hydroquinone compound, phosphite ester based compound or their substituent, mantoquita, iodide etc..Part antioxidant is favourable In promoting the polymerisation and suppress the gasification of 1,5- pentanediamines.

In the preparation method of nylon fiber of the invention, the environment temperature for concentrating nylon saline solution, i.e. thickener Temperature be preferably 80 DEG C~150 DEG C.The temperature being polymerized by nylon salt about at 190 DEG C~200 DEG C, therefore, at 80 DEG C Nylon salt in~150 DEG C of temperature ranges in thickener is simultaneously not apparent from polymerisation, it has been found that when temperature is more than 150 DEG C When, 1,5- pentanediamine is very fast with the speed that water volatilizees, accordingly, it would be desirable to the temperature of thickener is controlled no more than 150 DEG C, to reach Concentration and the dual purpose of suppression 1,5- pentanediamine volatilizations.Wherein, the temperature of thickener is more preferably 90 DEG C~140 DEG C.

Additionally, for the same reason, the environmental pressure for concentrating nylon saline solution, the i.e. pressure of thickener is preferably It is maintained in the range of 0.01 to 0.5MPa (gauge pressure), more preferably 0.03 to 0.3MPa.Thickener outlet nylon salt Concentration is preferably 70%~95%, on the one hand, the concentration of the nylon saline solution is preferably 70% weight or higher, because this is dense The more vaporization amount of 1,5- pentanediamines that degree can be protected in positive subsequent reactor.On the other hand, the concentration of the nylon saline solution is excellent Elect 95% weight or lower as, prepolymer can be so made in pressure controlling step.Therefore, at the end of concentration step, The concentration of nylon saline solution is more preferably 80%~90%.

In the preparation method of nylon fiber of the invention, for high pressure precondensation reactor pressure be preferably 0.5~ 2.2MPa (gauge pressure), unless otherwise noted, pressure of the present invention is gauge pressure.Certain pressure is maintained to be conducive in reactor Suppress the gasification of 1,5- pentanediamines, and cause that prepolymer is easily formed, while melt temperature is can guarantee that, and low pressure is conducive to water to steam The quick drain of gas.Therefore, reactor pressure is more preferably 0.8~1.7MPa (gauge pressure).Reactor outlet temperature is preferably 220 DEG C~260 DEG C, the too low meeting of temperature causes melt to solidify, reaction terminating, and temperature is too high easily to cause 1,5- pentanediamines to volatilize, side reaction Occur.Therefore, reactor outlet temperature is more preferably 230~250 DEG C.

The preparation method of nylon fiber of the invention, is additionally included in the step 3) after, step 4) forward direction prepolymer The step of middle addition additive, the additive can be various delustering agents for being not readily dissolved in water less than 10000ppm, dyestuff, anti- Electrostatic agent, fire retardant, metal and slaine etc., the performance for improving, changing the fiber of nylon 56.

In the preparation method of nylon fiber of the invention, for prepolymer flash distillation the preferred neighbour's phenylate of flash vessel as heating Medium, temperature control is at 260 DEG C~320 DEG C.Adjacent phenylate steam meets flash vessel requirement by condensing a large amount of latent heat of offer, while Control vapor (steam) temperature by vapour pressure causes side reaction to occur in order to avoid temperature is too high.Temperature for prepolymer flash distillation is further Preferably 270 DEG C~310 DEG C.

In the preparation method of nylon fiber of the invention, pre-polymerization device for normal pressure polycondensation, the vacuum polycondensation of prepolymer, The temperature range of post polymerizer is preferably 250 DEG C~290 DEG C, and the temperature must be maintained on melting point polymer, and high temperature is beneficial to anti- Should carry out, it is possible to increase the degree of polymerization, but cause side reaction again excessively simultaneously, molecular weight distribution is widened.Therefore the temperature is more preferably It is 260 DEG C~280 DEG C.

The vacuum of post polymerizer of the invention is preferably 0 to -0.09MPa (gauge pressure).Vacuumize the shifting for being conducive to moisture Remove, beneficial to the uniformity for keeping reaction, melt viscosity and polymer molecule can be improved in the case where reaction temperature is not improved Amount.Vacuum is adjusted according to the requirement of the fibre property of nylon 56, and the vacuum is more preferably 0~-0.07MPa (tables Pressure).

In the present invention, the temperature for the spinning manifold of spinning is preferably controlled in 260 DEG C~300 DEG C, more preferably 270 DEG C ~290 DEG C.Can be according to the shape in the hole of the cross sectional shape of the single fiber for constituting the filament to be manufactured selection spinning head.But, It is excellent if uniformly to discharge the polymer with the filament form with circular section shape in preference pattern of the invention Select 0.1 to 0.5 millimeter of aperture and 0.1 to 5 millimeter of hole length.

Additionally, the solidification method generally by using cold water or the solidification method cooling using cooling air are spun into fiber, but it is Suppression moisture absorption, preferably uses cooling air solidification.As cooling air, tool is more preferably used with the speed of 0.3 to 1 meter per second There are 15 to 25 DEG C of temperature and the air of 20 to 90% relative humidity to be cooled down.With the interior for carrying out melt spinning and stretching Temperature and humidity environment is similar to, 20 to 30 DEG C of temperature and alap relative humidity is preferred in the range of 20 to 70% 's.Additionally, in such a situation it is preferred to by temperature control in ± 3 DEG C and by humid control in ± 5%.Generation cooling is empty The device of gas can be uniflow type or ring-like, but in view of the uniform cooling between single fiber, ring-like is preferred.

First godet coiling speed of the invention is preferably 300 to 5000m/minute.Coiling speed be preferably 300 meters/ Minute is higher, because so can fully improve spinning tension is spun into waving for fiber to reduce.On the other hand, this batches speed Degree is preferably remained in proper range, because can so carry out height ratio stretching to provide high-strength filaments.Meanwhile, the first roller Coiling speed can reduce production cost soon, but higher to melt requirement.Species according to intensity requirement and silk is more preferably rolled up Velocity interval is taken for 500 to 4500 ms/min.Preferably 2000~6000 ms/min of winding speed.

Draw ratio of the invention is preferably 1 to 7 times.Draw ratio=winding speed/the first roller coiling speed.Take-up roll and the Multiple godets can be added drawing-off step by step is realized between one godet.Multistage drawing-off can be uniformly directed strand to be formed The compact crystal phase of orientation.

The preferred room temperature of the first godet-roller temperature is to 50 DEG C in the present invention, behind godet maximum temperature preferably 100 DEG C~180 ℃。

It is 1.2~3 according to the fiber molecule amount narrowly distributing of nylon 56 prepared by the method for the invention, continuously runs 10 days Without fracture of wire, lousiness phenomenon, yarn unevenness as little as 1~2%, with limited oxygen index very high, is 29~35%, and traditional Buddhist nun The limited oxygen index of dragon only has 26~28%.

According to the method for the invention prepare the fiber of nylon 56 have absorbed water faster and drainage rates compared with conventional nylon, Saturated water absorption can adjust crystallinity and be adjusted with the degree of orientation by spinning technique, maximum up to 12-15%.

Nylon fiber prepared by the present invention can be long filament or short fibre.

Present invention also offers a kind of nylon fiber product comprising above-mentioned nylon fiber, described nylon fiber product can Being yarn, woven fabric, looped fabric or non-woven fabrics etc..

The fiber of nylon of the invention 56 is preferably so that adipyl pentanediamine construction unit accounts for the fiber repeat unit of nylon 56 50% mole or more.On the basis of effect of the present invention is not damaged, the fiber of nylon 56 can contain being total to less than 50% mole Polycondensation monomer component, but preferably comprise more adipyl pentanediamine units because can so improve strand regularity so that into It is easier orientation in membrane process and crystallizes to provide the fiber of engineering properties and excellent heat resistance.Therefore, adipyl penta 2 Amine unit more preferably accounts for 70% mole or more, most preferably 90% mole or more.

The fiber of nylon of the invention 56 has the viscosity number of 120~280mL/g in 96% sulfuric acid.Viscosity number is used as molecular weight Index, the molecular weight of its representation polymer higher is higher, and molecular weight high causes that nylon fiber has intensity higher.This be because For if molecular weight is higher, the amount of the molecule chain end that per unit is present is smaller, then may be that the defect of fiber is fewer.Together When, because strand is more long, each strand interacts (physical entanglement, hydrogen bond, Van der Waals force etc.) with more strands, so that Obtain and uniformly shift spinning stress and tensile stress, therefore strand is uniformly directed during fiber is manufactured.On the other hand, exist Viscosity number in sulfuric acid preferably remains in proper range, because the melt spinning under appropriate spinning temperature may suppress the polymer Thermal decomposition in spinning-drawing machine, to ensure outstanding resultant yarn and suppress fibre staining.It is maintained at the viscosity number in proper range It is preferably as because thermal decomposition suppresses, distribution of low molecular weight (Mw/Mn) can be kept.The more preferably 140mL/g of the viscosity number ~260mL/g, optimum range is 150mL/g~240mL/g.

The method of the present invention can be obtained the nylon fiber with Narrow Molecular Weight Distribution, used as the index of molecular weight distribution (Mw/Mn) 1.2~3 are necessary for, wherein Mw represents weight average molecular weight, Mn represents number-average molecular weight.Weight average molecular weight is divided equally with number The ratio of son amount is smaller to mean that molecular weight distribution is narrower.It is 3 or lower to have the viscosity number in sulfuric acid and Mw/Mn high as described above Narrow Molecular Weight Distribution the fiber of nylon 56 be preferably as can so obtain with high intensity, without broken end, good spinnability Fiber.Original because if Mw/Mn is small, then the interaction force of the strand that interacts and each strand (physical entanglement power, Hydrogen bond force, Van der Waals force etc.) become roughly equal, so that spinning stress and tensile stress are uniformly applied to respectively in film forming procedure On strand, therefore, the strand of noncrystalline phase is uniformly directed to form the oriented crystalline phase of many high compactions.

Further, since the effect of the strand being uniformly directed, exists for the crystalline phase that interlinks in amorphous phase Many amorphous chains (interconnection molecular), and the molecular chain length of the interconnection molecular is equal.Therefore, many of which is estimated with tension shape State is present (motion is limited by crystalline phase).That is, because the oriented crystalline containing many high compactions is mutually and by being permitted The interconnection molecular connection of many tensionings, they act synergistically to provide the fiber of nylon 56 with high intensity, low defect.

Mw/Mn is preferably 2.6 or lower, especially preferably 2.4 or lower.1.2 or higher ratio is to realize production institute The level for needing.The present inventor make further investigation and consequently found that, as the raw material of nylon 56 pentanediamine in the course of the polymerization process Volatile, crystallinity is less than conventional nylon 66, and it is not very high more importantly to melt storage stability, by cooling down repeatedly, Heating melting molecular weight may broaden, thus be difficult to make in spinning and drawing process strand be uniformly directed and trigger fine hair and Fracture of wire.The present invention is successfully solved by the way that directly fused mass directly spinning shortens melt in high-temperature residence time after technology controlling and process and polymerization This problem.

The nylon fiber of the invention preferably single fiber fineness with 0.1~10dtex.According to the difference of application field, this hair Bright device and technique can adjust filament number.Due to anomalies such as the too low easy appearance broken ends of filament number, while monofilament is fine Spend high and fabric bending strength can be caused too high, Boardy Feeling.Therefore, the single fiber fineness more preferably model of nylon fiber of the invention It is 1~8dtex to enclose, and most preferred range is 1.5~7dtex.Meanwhile, if above-mentioned filament number is maintained at invention claimed range It is interior, then suitable filament number can be selected according to purposes, to meet application requirement.

The intensity of the fiber of nylon of the invention 56 is preferably 3~12cN/dtex.Intensity is too low, easily goes out in weaving process Existing fine hair, finished product cracky, intensity is too high, and spinnability is poor during spinning, fracture of wire phenomenon easily occurs, according to the difference using field, Adjusted by polymerization and spinning technique, PA56 more preferably strength range is 4~10cN/dtex.

Used as filament of the invention, the shape of cross section of monofilament can be various forms, such as circle, Y types, multi-leaf-shaped, many Side shape, planar in form, hollow form and square cross form, but there is higher intensity and more low-permeable due to that can stablize to obtain Woven fabric, circular or planar in form is preferred.Circle is most preferably.The cross-sectional form of each fiber can be with mutually the same Or it is different but preferably identical.

As each fiber of the invention, in the degree for not damaging Expected Results of the invention, it is possible to use composite fibre (single, multicore or part exposure core) or bimetallic composite fibre, or can also use fine with the alloy of another polymer alloy Dimension.On the filament with higher-strength, the fiber only containing the component of nylon 56 is preferred.For example, it is (poly- right to enumerate polyester PET, PTT, polybutylene terephthalate (PBT), poly- naphthalenedicarboxylic acid ethylene glycol Ester, PLA etc.), (polyamide m, such as polyamide 6, carbon number m in each repeat unit are 4 to 12, polyamide to polyamide Mn, such as polyamide 66, carbon number m in each repeat unit are 4 to 12, and carbon number n is 4 to 12, etc.), makrolon, Polystyrene, polypropylene, polyethylene, polyformaldehyde, polymethyl methacrylate, polyethylene glycol etc..Can be by appropriate selection homopolymerization Thing, copolymer (comprising the component that is set forth below as comonomer above-mentioned polymer) etc..

Additionally, filament of the invention can also mix with other fibers, spinning or stranded.The example of other fibers includes day Right fiber, such as cotton, fiber crops, hair and silk, such as regenerated fiber, artificial silk and cuprammonium rayon, such as semisynthetic fibre, acetic acid esters, and contain Have homopolymers and copolymer (comprising the component being set forth below as comonomer above-mentioned polymer) form polyamide (polyamides Amine m, such as polyamide 6, the carbon number m in each repeat unit are 4 to 12, polyamide mn, such as polyamide 66, in each repeat unit Carbon number m be 4 to 12, carbon number n is 4 to 12, etc.), polyester it is (polyethylene terephthalate, poly- to benzene two Formic acid propylene glycol ester, polybutylene terephthalate (PBT), PLA etc.), polyacrylonitrile, polypropylene, the synthesis of polyvinyl chloride etc. Fiber.

The filament of nylon of the invention 56 can also contain the following components less than 10% weight.Such as antioxidant, heat-resisting Stabilizer (compound, the compound based on quinhydrones, the compound based on thiazole, the compound based on phosphorus based on hindered phenol, such as Phenyl-phosphonic acid, the compound based on imidazoles, such as 2-mercaptobenzimidazole, its substitution product, copper halide, iodine compound), it is weather-proof Agent (based on resorcinol, salicylate, BTA, benzophenone, hindered amine etc.), pigment (cadmium sulfide, phthalocyanine, carbon black Deng), gloss enhancer (titanium oxide, calcium carbonate etc.), dyestuff (Ni Gehei, nigrosine etc.), crystal nucleating agent (talcum, titanium dioxide Silicon, kaolin, clay etc.), plasticizer (to oxybenzoic acid monooctyl ester, N-butylbenzenesulfonamide etc.), antistatic additive (alkyl sulfate Type anionic antioxidant, quaternary ammonium salt cationic type antistatic additive, such as non-ionic antistatic agent, polyoxyethylene sorbitol Alcohol acid anhydride monostearate, the both sexes antistatic additive based on glycine betaine etc.), fire retardant (melamine cyanurate, hydroxide, Such as magnesium hydroxide or aluminium hydroxide, ammonium polyphosphate, brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, brominated oxygen tree Fat, the combination being made up of any these fire retardants and antimony oxide for being based on bromine etc.).

Further, nylon of the invention 56 can also be in the degree for not damaging the object of the invention and except 1,5- pentanediamines With other copolymer compounds outside adipic acid, and such as construction unit derived from following component can be contained：

Aliphatic carboxylic acid (oxalic acid, malonic acid, butanedioic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, hendecane Diacid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, octadecane diacid etc.), alicyclic dicarboxylic acid (cyclohexyl dicarboxylic acid etc.) and aromatic dicarboxylic acid (terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, anthracene dicarboxyl Acid, luxuriant and rich with fragrance dicarboxylic acids, diphenyl ether dicarboxylic acids, diphenoxyethanedicarboxylic acid, diphenylethane dicarboxylic acids, 1,4- hexamethylene dicarboxyls Acid, 5- sodiosulfoisophthalic acids, 5- 4-butyl-phosphonium M-phthalic acids etc.).

Additionally, nylon of the invention 56 can contain derived from aliphatic diamine, such as ethylenediamine, 1,3- diaminopropanes, Isosorbide-5-Nitrae- Diaminobutane, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonanes, 1,10- Diamino decane, 1,11- diamino undecanes, 1,12- diamino dodecanes, 1,13- diaminourea tridecane, 1,14- diaminourea The tetradecane, 1,15- diaminourea pentadecane, 1,16- diaminourea hexadecane, 1,17- diaminourea heptadecane, 1,18- diaminourea 18 Alkane, 1,19- diaminourea nonadecane, 1,20- diaminourea eicosane or 2- methyl isophthalic acids, 5- pentanediamines, such as alicyclic diamine, hexamethylene two Amine or double-(4- Aminohexyls) methane, or aromatic diamine, such as construction unit of benzene dimethylamine.

Nylon of the invention 56 can contain derived from aromatics, aliphatic series or alicyclic diol compound, such as ethylene glycol, the third two Alcohol, butanediol, pentanediol, hexylene glycol, 1,4- cyclohexanedimethanols, neopentyl glycol, quinhydrones, resorcinol, dihydroxybiphenyl, naphthalene two Alcohol, anthracene glycol, luxuriant and rich with fragrance glycol, the construction unit of double (4- hydroxy phenyls) propane, 4,4 '-dihydroxydiphenyl ether or the bisphenol Ss of 2,2-.

Nylon of the invention 56 can contain aromatics, aliphatic series or the alicyclic ring for having hydroxyl and carboxylic acid derived from each compound Race's hydroxycarboxylic acid, such as lactic acid, 3- hydroxy propionates, 3-hydroxybutyrate ester, 3-hydroxybutyrate ester-valerate, hydroxybenzoic acid, hydroxyl The construction unit of base naphthalene-carboxylic acid, hydroxyl anthracene carboxylic acid, hydroxyl phenanthrene carboxylic acid or (hydroxy phenyl) vinyl carboxylic acid.

Polyamide of the invention 56 further can contain derived from amino acid, such as 6-aminocaprolc acid, 11- amino-undecanoics Acid, 12 amino dodecanoic acid or PAMBA or lactams, such as structure of epsilon-caprolactams or ε-lauric lactam Unit.

Therefore, the method for the present invention, can also add other comonomers and 1,5- pentanediamine, adipic acid copolymerization, it is described its Its comonomer be selected from amino acid, lactams, aromatics, aliphatic series, alicyclic dicarboxylic acid, aromatics, aliphatic series, alicyclic diol, aromatics, Aliphatic series, alicyclic diamine, one or more in aromatics, aliphatic series, cycloaliphatic hydroxyl group carboxylic acid, and the derivative of above-mentioned monomer, Wherein, the derivative of above-mentioned monomer includes the product of above two monomer reaction, for example, an amino of a molecule diamines With a carboxyl reaction of a molecule dicarboxylic acids into salt product.

The fiber of nylon of the invention 56 has excellent engineering properties, heat resistance, wearability and durability, can serve as various Fibre structure, such as fabric (Woven fabric, knitted fabric, supatex fabric, pile), rope (rubberized cord, rope, band, fishing Net, braid over braid etc.), and it is widely used in industrial use and apparel applications.For example, they are suitable as constituting indoor and outdoors material Material and the vehicles (such as automobile and aircraft) safety component, including air bag, rubber reinforcement fiber, seat harness, sheet material, pad The fibre structure of son etc..

Further, they are applied to industrial use, such as fishing net, rope, safety belt, hoist cable, oil skin, tent, bag Fabric, braid over braid, protection board, canvas, sewing thread etc., agricultural protect cloth, construction material waterproof cloth etc. with turf.

Additionally, they are applicable to need the apparel applications of intensity and wearability, such as outdoor clothing and sport clothing.On ground Blanket field, can be used to produce bulk filament, for producing polyamide tufted carpet.The fibre structure can containing the fiber of nylon 56 with Outer fiber, but in order to using the excellent properties of the fiber of nylon 56 of the invention, the content of the fiber of nylon of the invention 56 is preferred It is 50% weight or more.More preferably 70% weight or more, still more preferably from 90% weight or more.

Below, in conjunction with specific embodiments, nylon fiber of the invention and preparation method thereof is described further.Ying Li Solution, following examples are merely to illustrate the present invention not for limitation the scope of the present invention.

Wherein, following performance characterization has been carried out to the fiber of nylon of the invention 56 in following embodiments：

1st, viscosity number

Ubbelohde viscometer sulphate method：Precise 0.25 ± 0.0002g of dried nylon66 fiber sample, adds 50mL dense Sulfuric acid (96%) dissolves, and measures in 25 DEG C of constant temperature water baths and record concentrated sulfuric acid flow time t0 and when nylon66 fiber solution is flowed through Between t.

Viscosity number computing formula：Viscosity number VN=(t/t0-1)/C；

T-solution flow time；

T0-solvent flow time；

The concentration (g/mL) of C-polymer.

2nd, molecular weight distribution

With 90 DEG C of hot wash fiber samples 30 minutes, and dry at 90 DEG C in a vacuum, to realize that 1000ppm water contains Amount.Dissolve a sample in hexafluoroisopropanol to obtain testing liquid.It passes through gel permeation chromatography (GPC) measurement to obtain Weight average molecular weight and number-average molecular weight (Mn) in terms of PMMA (Mw), finally obtain Mw/Mn.Measuring condition is as follows：

GPC instruments：Waters 510；

Post：Two Shodex GPC HFIP-806M posts of connection；

Solvent：Hexafluoroisopropanol；

Temperature：30℃；

Flow velocity：0.5 ml/min；

Sample concentration：2 milligrams/4 milliliters；

Filtering：0.45μm-DISMIC 13HP(Toyo Roshi)；

Injection volume：100μl；

Detector：Differential refractometer RI (Waters 410)；

Standard specimen：PMMA (concentration：1 milliliter of 0.25 milligram/solvent of sample)；

Time of measuring：62 minutes.

3rd, fiber number

Determined by GB/T14343-2003 methods.

4th, strength

Determined by GB/T14344-2008 methods.

5th, elongation

Determined by GB/T14344-2008 methods.

6th, broken yarn number of times

Count and the broken yarn number of times occurred during double centner filament is formed by spinning and stretching.Less broken yarn number of times is considered as It refer to more preferable spinnability.

7th, limited oxygen index

Determined by ISO 4589-2 methods.

8th, saturated water absorption

First the drying 12 hours of 120 DEG C of fiber sample electricity consumption vacuum drying oven, natural cooling 2 hours in drier are put into, Weigh respectively during about 10g samples are put into 98.5 DEG C of water-baths and be incubated 2 hours, soaked 15 minutes with cold pure water afterwards, take out aqueous fibre Dimension, first with filter-cloth filtering, then wipes surface moisture with cotton again, is finally dried again with filter paper and weighed.

Saturated water absorption=(fiber wet weight-fiber dry weight)/fiber dry weight × 100%.

9th, yarn unevenness

Determined by GB/T 14346-93 methods.

Embodiment

Embodiment 1

1,5- pentanediamines and adipic acid be made into 60% 5 tons of the aqueous solution in into salt oven 1, pH value adjusts to 7.6 that (salt is molten Liquid is diluted to 10% testing result), temperature control is transferred to pans 2 at 50 DEG C through filter, then through the first preheater 3 heating-up temperatures are further concentrated into 80% concentration after rising to 90 DEG C into thickener 4, and the outlet temperature of thickener 4 is 120 DEG C, molten Liquid enters reactor 6 after the second preheater 5 is further heated to 213 DEG C, and the pressure of reactor 6 is 1.73MPa, outlet temperature At 240 DEG C, by cooling tower recycling, reaction solution subsequently enters the removing most of moisture of flash vessel 8, pressure to steam for control It is down to normal pressure.Eventually pass pre-polymerization device 9, the completion of post polymerizer 10 polymerisation and obtain the melt of nylon 56, forward and backward polymerizer folder Set heat conduction oil temperature is 280 DEG C, and wherein pre-polymerization device 9 is normal pressure, and the vacuum of post polymerizer 10 is -0.02MPa (gauge pressure).It is whole Individual polymerization process keeps nitrogen protection.

The melt of nylon 56 that continuous polymerization is obtained is evenly distributed in filament spinning component through spinning pump accurate measurement, is spun Silk casing 11 temperature is 280 DEG C.Sprayed through spinneret and turn into melt stream, the hole diameter of spinneret is 0.35mm, and length is 0.7mm, hole count is 72 holes.By the cooling shaping of cross air blowing device 12,21 DEG C of the wind-warm syndrome of cross air blowing device 12, rheumatism 65%, wind Fast 0.3m/s.The tow of cooling forming is drawn to the first seal wire by after spinning shaft 13, being oiled through the boundling of oiling device 14 Roller 15, is fallen strand from spinneret with certain speed, obtains undrafting wire (UDY) or preoriented yarn (POY), preoriented yarn Bar is out drawn to the second godet 16 afterwards from the first seal wire 15, and subsequently into winch spool 17, finished silk is wound on winch spool On 17, spinning cake is wound on the winder, be made the undrawn yarn of nylon 56.Winding speed is 1000m/min.Through performance detection, Result is shown in table 1.

Embodiment 2

1,5- pentanediamines and adipic acid be made into 60% 5 tons of the aqueous solution in into salt oven 1, pH value adjusts to 7.6 that (salt is molten Liquid is diluted to 10% testing result), then add the salt weight of 5% nylon 56 nylon salt, temperature control at 50 DEG C, through filter turn Move to pans 2, then be further concentrated into 80% into thickener 4 after rising to 90 DEG C through the heating-up temperature of the first preheater 3 Concentration, the outlet temperature of thickener 4 is 120 DEG C, and solution enters reactor after the second preheater 5 is further heated to 213 DEG C 6, the pressure of reactor 6 is 1.73MPa, outlet temperature control at 240 DEG C, steam by cooling tower recycling, reaction solution with Enter flash vessel 8 afterwards and remove most of moisture, pressure is down to normal pressure.Forward and backward polymerizer completion polymerisation is eventually passed to obtain The melt of nylon 56, forward and backward polymerizer chuck heat conduction oil temperature is 275 DEG C, and wherein pre-polymerization device 9 is normal pressure, post polymerizer 10 Vacuum is -0.04MPa (gauge pressure).Whole polymerization process keeps nitrogen protection.

The melt of nylon 56 that continuous polymerization is obtained is evenly distributed in filament spinning component through spinning pump accurate measurement, is spun Silk case temperature is 278 DEG C.Sprayed through spinneret and turn into melt stream, the hole diameter of spinneret is 0.35mm, and length is 0.7mm, hole Number is 72 holes.By the cooling shaping of cross air blowing device 12,21 DEG C of the wind-warm syndrome of cross air blowing device 12, rheumatism 65%, wind speed 0.3m/s. The tow of cooling forming is wound into spinning cake on the winder by after spinning shaft 13, being oiled through the boundling of oiling device 14, is made The undrawn yarn of nylon 56.Winding speed is 1000m/min.Through performance detection, table 1 is as a result shown in.

Embodiment 3

1,5- pentanediamines and adipic acid be made into 65% 5 tons of the aqueous solution in into salt oven 1, pH value adjusts to 8.0 that (salt is molten Liquid is diluted to 10% testing result), temperature control is added thereto to 10ppm (relative to nylon salt weight) Bu Lvge at 50 DEG C Graceful antioxidant, pans 2 are transferred to through filter, then enter concentration after rising to 90 DEG C through the heating-up temperature of the first preheater 3 Groove 4 is further concentrated into 80% concentration, and the outlet temperature of thickener 4 is 120 DEG C, and solution is by the second further heating of preheater 5 Enter reactor 6 after to 213 DEG C, the pressure of reactor 6 is 1.3MPa, and at 242 DEG C, steam is returned by cooling tower for outlet temperature control Receive and recycle, reaction solution subsequently enters the removing most of moisture of flash vessel 8, pressure is down to normal pressure.Eventually pass forward and backward polymerizer Complete polymerisation and obtain the melt of nylon 56, forward and backward polymerizer chuck heat conduction oil temperature is 278 DEG C, and wherein pre-polymerization device 9 is Normal pressure, the vacuum of post polymerizer 10 is -0.06MPa (gauge pressure).Whole polymerization process keeps nitrogen protection.

The melt of nylon 56 that continuous polymerization is obtained is evenly distributed in filament spinning component through spinning pump accurate measurement, is spun Silk case temperature is 280 DEG C.Sprayed through spinneret and turn into melt stream, the hole diameter of spinneret is 0.25mm, and length is 0.6mm, hole Number is 72 holes.By the cooling shaping of cross air blowing device 12,21 DEG C of the wind-warm syndrome of cross air blowing device 12, rheumatism 75%, wind speed 0.38m/ s.The tow of cooling forming by after spinning shaft 13, being oiled through the boundling of oiling device 14, the spinning speed for being used for 3200m/min, obtains preliminary draft silk.Through performance detection, table 1 is as a result shown in.

Embodiment 4

1,5- pentanediamines and adipic acid be made into 70% 5 tons of the aqueous solution in into salt oven 1, pH value adjusts to 8.2 that (salt is molten Liquid is diluted to 10% testing result), temperature control is added thereto to 50ppm (relative to nylon salt weight) Bu Lvge at 50 DEG C Graceful antioxidant, pans 2 are transferred to through filter, then enter concentration after rising to 90 DEG C through the heating-up temperature of the first preheater 3 Groove 4 is further concentrated into 80% concentration, and the outlet temperature of thickener 4 is 120 DEG C, and solution is by the second further heating of preheater 5 Enter reactor 6 after to 213 DEG C, the pressure of reactor 6 is 1.0MPa, and at 241 DEG C, steam is returned by cooling tower for outlet temperature control Receive and recycle, reaction solution subsequently enters the removing most of moisture of flash vessel 8, pressure is down to normal pressure.Eventually pass forward and backward polymerizer Complete polymerisation and obtain the melt of nylon 56, forward and backward polymerizer chuck heat conduction oil temperature is 278 DEG C, and wherein pre-polymerization device 9 is Normal pressure, the vacuum of post polymerizer 10 is -0.06MPa (gauge pressure).Whole polymerization process keeps nitrogen protection.

The melt of nylon 56 that continuous polymerization is obtained is evenly distributed in filament spinning component through spinning pump accurate measurement, is spun Silk case temperature is 280 DEG C.Sprayed through spinneret and turn into melt stream, the hole diameter of spinneret is 0.25mm, and length is 0.6mm, hole Number is 72 holes.By the cooling shaping of cross air blowing device 12,21 DEG C of the wind-warm syndrome of cross air blowing device 12, rheumatism 83%, wind speed 0.35m/ s.The tow of cooling forming by after spinning shaft, being oiled through the boundling of oiling device 14, batch by 40 DEG C of 15 temperature of the first godet Speed is 2700m/min, then after through multiplying power being 1.5 stretching, follow-up godet maximum temperature is set to 140 DEG C, on the winder Spinning cake is wound into, the full-drawn yarn of nylon 56 is made.The winding speed for being used is 4000m/min.Through performance detection, as a result it is shown in Table 1.

Embodiment 5

1,5- pentanediamines and adipic acid be made into 75% 5 tons of the aqueous solution in into salt oven 1, pH value adjusts to 7.6 that (salt is molten Liquid is diluted to 10% testing result), temperature control is transferred to pans 2 at 80 DEG C through filter, then through the first preheater 3 heating-up temperatures are further concentrated into 80% concentration after rising to 90 DEG C into thickener 4, and the outlet temperature of thickener 4 is 120 DEG C, molten Liquid enters reactor 6 after the second preheater 5 is further heated to 213 DEG C, and the pressure of reactor 6 is 0.5MPa, outlet temperature At 240 DEG C, by cooling tower recycling, reaction solution subsequently enters the removing most of moisture of flash vessel 8, pressure to steam for control It is down to normal pressure.Eventually pass forward and backward polymerizer completion polymerisation and obtain the melt of nylon 56, forward and backward polymerizer chuck conduction oil Temperature is 282 DEG C, and wherein pre-polymerization device 9 is normal pressure, and the vacuum of post polymerizer 10 is -0.06MPa (gauge pressure).Entirely it was polymerized Journey keeps nitrogen protection.

The melt of nylon 56 that continuous polymerization is obtained is evenly distributed in filament spinning component through spinning pump accurate measurement, is spun Silk case temperature is 285 DEG C.Sprayed through spinneret and turn into melt stream, the hole diameter of spinneret is 0.4mm, and length is 0.8mm, hole count It is 500 holes.By the cooling shaping of cross air blowing device 12,21 DEG C of the wind-warm syndrome of cross air blowing device 12, rheumatism 83%, wind speed 0.32m/s. The tow of cooling forming is wound into spinning cake, Ran Houjing on the winder by after spinning shaft, being oiled through the boundling of oiling device 14 After boundling, stretching, curling, thermal finalization, the chopped fiber of nylon 56 is cut into.Winding speed is 800m/min.Through performance test, as a result It is shown in table 1.

Embodiment 6

1,5- pentanediamines and adipic acid be made into 65% 5 tons of the aqueous solution in into salt oven 1, pH value adjusts to 7.8 that (salt is molten Liquid is diluted to 10% testing result), temperature control is transferred to pans 2 at 60 DEG C through filter, then through the first preheater 3 heating-up temperatures are further concentrated into 90% concentration after rising to 90 DEG C into thickener 4, and the outlet temperature of thickener 4 is 130 DEG C, molten Liquid enters reactor 6 after the second preheater 5 is further heated to 215 DEG C, and the pressure of reactor 6 is 1.2MPa, in reactor 6 By additive tank 7 by the titanium dioxide aqueous solution of injection 11% in melt, titanium dioxide is nylon salt weight in exit 2500ppm, at 242 DEG C, by cooling tower recycling, reaction solution subsequently enters flash vessel 8 and takes off steam for outlet temperature control Except most of moisture, pressure is down to normal pressure.Eventually pass forward and backward polymerizer completion polymerisation and obtain the melt of nylon 56, it is forward and backward Polymerizer chuck heat conduction oil temperature is 278 DEG C, and wherein pre-polymerization device 9 is normal pressure, and the vacuum of post polymerizer 10 is -0.06MPa (gauge pressure).Whole polymerization process keeps nitrogen protection.

The melt of nylon 56 that continuous polymerization is obtained is evenly distributed in filament spinning component through spinning pump accurate measurement, is spun Silk case temperature is 280 DEG C.Sprayed through spinneret and turn into melt stream, the hole diameter of spinneret is 0.25mm, and length is 0.6mm, hole Number is 72 holes.By the cooling shaping of cross air blowing device 12,21 DEG C of the wind-warm syndrome of cross air blowing device 12, rheumatism 75%, wind speed 0.38m/ s.The tow of cooling forming by after spinning shaft 13, being oiled through the boundling of oiling device 14, the spinning speed for being used for 3000m/min, obtains preliminary draft silk.Through performance detection, table 1 is as a result shown in.

Comparative example 1

Dry from table mountain Shen Ma engineering plastics Co., Ltd and buy nylon 66 slice 50kg, be continuously fed into single screw rod extruding It is heated, extrude, be melt into PA66 fused mass in machine, single screw extrusion machine zonal control, area's heating-up temperature 255 vertically DEG C, 280 DEG C of two area's heating-up temperature, 285 DEG C of three-zone heating temperature, four 295 DEG C of area's heating-up temperatures, five 308 DEG C of area's heating-up temperatures, six 294 DEG C of area's heating-up temperature, 290 DEG C of spinning body temperature.It is accurate through the spinning pump in melt distribution pipe to spinning manifold again Metering, through waiting long tube that nylon66 fiber fused mass melt is evenly distributed in filament spinning component, measuring pump quantity delivered 60g/min, its turn Number 25r/min.The external diameter of circular spinneret is 70mm, and spinneret hole count is 48 holes, and spinneret aperture is 0.3mm.In filament spinning component The melt for mixing sprays from spinneret, sprays to form filament from the spinneret high pressure of filament spinning component bottom, and filament exists Cooling shaping under conditions of the cross air blasting of constant temperature and humidity, 20 DEG C of the wind-warm syndrome of cross air blasting, rheumatism 75%, wind speed 0.38m/s.It is cooled to The tow of shape is rolled up on the winder by after spinning shaft, being oiled through oiling device boundling, then after through multiplying power being 1.5 stretching Spinning cake is coiled into, nylon66 fiber fully drawn yarn is made.The spinning speed for being used is 4000m/min.Through performance test, table is as a result shown in 1。

Comparative example 2

Dry and beautiful can be continuously fed into single-screw extrusion machine up to purchase nylon 6 slice 50kg from newly, it is heated, extruding, molten Melt into PA6 fused mass, single screw extrusion machine zonal control vertically, 240 DEG C of area's heating-up temperature, 275 DEG C of two area's heating-up temperature, 285 DEG C of three-zone heating temperature, four 290 DEG C of area's heating-up temperatures, five 295 DEG C of area's heating-up temperatures, six 288 DEG C of area's heating-up temperatures, spinning 286 DEG C of spin manifold temperature.Again through the spinning pump accurate measurement in melt distribution pipe to spinning manifold, through waiting long tube by nylon 56 Fused mass melt is evenly distributed in filament spinning component, measuring pump quantity delivered 60g/min, its revolution 25r/min.Circular spinneret External diameter is 70mm, and spinneret hole count is 48 holes, and spinneret aperture is 0.3mm.The melt mixed in filament spinning component is from spinneret Spray, spray to form filament from the spinneret high pressure of filament spinning component bottom, condition of the filament in the cross air blasting of constant temperature and humidity Lower cooling shaping, 20 DEG C of the wind-warm syndrome of cross air blasting, rheumatism 75%, wind speed 0.38m/s.The tow of cooling forming is by spinning shaft Afterwards, oiled through oiling device boundling, then after through multiplying power being 1.5 stretching, spinning cake is wound on the winder, be made nylon 6 complete Drawn yarn.The spinning speed for being used is 4000m/min.Through performance test, table 1 is as a result shown in.

Table 1, performance test

Above example is the explanation to technical scheme, and the limitation to present aspect technical scheme is not constituted.This area Technical staff according to the knowledge of existing nylon preparation method, can by the raw material proportioning in preparation process, preparation process Temperature, pressure adjustment, realize the preparation of the nylon of different viscosity numbers.

Although having represented and having discussed some aspects of the invention, those skilled in the art should realize Arrive, above-mentioned aspect can be changed under conditions of without departing substantially from the principle of the invention and spirit, therefore the scope of the present invention will Limited by claim and equivalent content.

Claims (10)

1. a kind of preparation method of nylon fiber, including after polymerisation will be carried out comprising the raw material of 1,5- pentanediamines and adipic acid Directly carry out spinning.

2. method according to claim 1, wherein, the polymerisation comprises the following steps：

1) 1,5- pentanediamines and adipic acid are made into nylon saline solution；

2) the nylon saline solution is concentrated；

3) by the nylon saline solution precondensation after concentration, prepolymer is obtained；

4) by the further dehydration polymerization of the prepolymer, the melt of nylon 56 is obtained.

3. method according to claim 1, wherein, the spinning includes：

A) melt after polymerisation is sprayed through spinneret, forms melt stream；

B) melt stream solidifies out into strand through blowing；

C) tow collecting machine is oiled；

D) strand is obtained into nylon fiber through drawing-off and post-processing.

4. method according to claim 2, wherein, the step 1) nylon saline solution in the mass fraction of nylon salt be 55%~80%；And/or

The step 1) pH value of nylon saline solution when being diluted to 10% be 7~9.

5. method according to claim 2, wherein, also including adding other comonomers and/or additive the step of, it is described to add Plus agent is selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, pigment, gloss enhancer, dyestuff, crystal nucleating agent, delustering agent, plasticising One or more in agent, antistatic additive, fire retardant, metal and slaine；

Described other comonomers can be selected from amino acid, lactams, aromatics, aliphatic series, alicyclic dicarboxylic acid, aromatics, aliphatic series, fat Ring race glycol, aromatics, aliphatic series, alicyclic diamine, in aromatics, aliphatic series, cycloaliphatic hydroxyl group carboxylic acid, and above-mentioned monomer derived thing One or more.

6. method according to claim 2, wherein, the temperature of the concentration step is 80 DEG C~150 DEG C, pressure be 0.01 to 0.5MPa；And/or

The mass fraction that the nylon saline solution is concentrated into the nylon salt is preferably 70%~95%, more preferably 80%~90%.

7. method according to claim 2, wherein, the pressure of the precondensation steps is preferably 0.5~2.2MPa, further excellent Elect 0.8~1.7MPa as；And/or

The dehydration polymerization step includes flash distillation, and the flash temperature is 260 DEG C~320 DEG C；And/or

The temperature of the dehydration polymerization is 250 DEG C~290 DEG C, and pressure is 0 to -0.09MPa.

8. the nylon fiber that prepared by the method according to claim any one of 1-7.

9. nylon fiber according to claim 8, wherein, adipyl pentanediamine construction unit accounts for the nylon fiber repeat unit At least 50%；And/or

The nylon fiber includes the copolymer formed by 1,5- pentanediamines, adipic acid and other monomer copolymerizations, described other lists Body is selected from amino acid, lactams, aromatics, aliphatic series, alicyclic dicarboxylic acid, aromatics, aliphatic series, alicyclic diol, aromatics, aliphatic series, fat Ring race diamines, one or more in aromatics, aliphatic series, cycloaliphatic hydroxyl group carboxylic acid, and above-mentioned monomer derived thing.

10. a kind of nylon fiber product, wherein, comprising the nylon fiber described in claim 8 or 9.