CN102206338A - Nylon 66 resin, nylon 66 filament and preparation method thereof - Google Patents
Nylon 66 resin, nylon 66 filament and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the spinning material field, and particularly provides a nylon 66 resin which is prepared by mixing nylon 66 salt melt and rare earth metal compounds and performing a polymerization reaction and a post-polycondensation reaction, wherein according to the weight of the nylon 66 salt, the weight of the rare earth metal compounds is 0.01-0.8%. The invention also provides a nylon 66 filament which is prepared by the nylon 66 resin and is obtained by melt spinning of the nylon 66 resin. By using the nylon 66 resin and the preparation method of the invention, a fine denier or ultrafine denier nylon 66 filament can be obtained with a denier of 0.10-1.0 dtex; both the fiber strength and the elongation at break meet the post-weaving requirements; the invention fills a gap at home and abroad that fine denier or ultrafine denier nylon 66 filaments can be produced by a conventional high-speed spinning method, and increases the technological content and the added value of nylon 66 fiber products.
Description
Technical field
The present invention relates to the spinning material field, relate in particular to and be specifically designed to a kind of Nylon 66 of producing thin dawn or super fine denier nylon 66 long filaments, nylon 66 long filaments and preparation method thereof.
Background technology
In general, can the weave macromolecular material of usefulness comprises nylon (polymeric amide), polypropylene, polyethylene terephthalate and polyacrylonitrile etc.These materials can form fiber by spinning processing and be called polyamide fibre, polypropylene fibre, terylene and acrylic fibers etc., thereby are used for textile industry.Melt-spinning is a kind of spinning processes commonly used, by melt-spinning can obtain being suitable for weaving each fibrid of usefulness.Usually, use the filament number of the fiber that melt spinning method obtains to reach 1.0dtex.With the fibrous woven of such fiber number product, for example garment material etc. have lot of advantages, so the application space, market is wide.
Yet, also more and more higher along with the raising of people's living standard for the requirement of textiles, be starved of some existing defectives that can overcome textiles.For example, above-mentioned mention such as products such as garment materials, because therefore its fiber yarn slightly exists that feel is coarse, flexibility is poor, ventilation property is poor, water-absorbent is poor, is easy to problem such as pilling.In order to address these problems, it is an important subject that the thin dawn of textile fibres or super fine denier change into.
At present, carried out a lot of researchs, and a lot of relevant reports have been arranged about thin dawn of textile fibres or super fine denierization.For example, on the Chinese side, thin dawn of trevira or super fine denier technology in last century the eighties succeed in developing.The thin dawn of polypropylene fibre or super fine denierization in last century the nineties develop by the Chinese Academy of Sciences chemistry Xu Duan husband academician of institute, this technology has realized industrialization at present, and correlation technique information is to describe to some extent in the Chinese patent literature of CN1073595A, CN1058062A, CN1076032A and CN1068075A at publication number.
But for nylon fiber, the technology of utilization fusion direct fabrics method manufacturing (surpassing) fine denier nylon fiber is still immature.
Characteristics such as the nylon fiber fabric has absorbing sweat, lightweight, toughness is good, rebound resilience good, antiacid alkali are best suited for one of man-made fabric of human dress, and the application on clothes also is one of main application of nylon fiber.The thickness of nylon fiber can be characterized with filament number, usually, filament number be man-made fiber about 1.1dtex fine count fiber, and filament number to be man-made fiber about 0.55dtex be called superfine Denier fibre.Nylon fiber is thin more, and the snugness of fit of its fabric is good more.Thin dawn or superfine denier nylon fibre can be made into soft, comfortable and easy to wear high-grade yarn fabric, and very high economic worth is arranged.Thereby the exploitation of fine count fiber and superfine Denier fibre manufacturing technology is the new and high technology all paid attention to of each state in recent years.If can realize fusion direct fabrics method thin dawn of manufacturing or superfine denier nylon fibre, that will open up another wide Application Areas for textile industry.
The diameter of fine count fiber and superfine Denier fibre is much thinner than conventional chemical fiber (filament number is generally 2.2dtex-6.6dtex), and the technical difficulty of making this class man-made fiber is quite big, need select appropriate spinning material and auxiliary agent for use.Also need choose reasonable spining technology scheme and every production processes such as strict control spinning, drawing-off.
Yet up to the present, the report that improves the research of nylon spinning property by modification mode is also few, thereby the main aspect of modification is by copolymerization or adds auxiliary agent and reduce the extension ability that the molecular orientation of nylon when reeling improves monofilament.For example, (1) introduces asymmetric cell by copolymerization, reducing the ability of molecular orientation, as, add the caprolactam and the piperidine of asymmetric diprotic acid, diamine or band side group during common nylon polymerization; (2) when spinning, add acrylic acid derivative, as the methyl methacrylate polyester; (3) the employing long-chain nylon carries out spinning or add long-chain nylon and salt thereof or the like when the monomer polymerization of matrix nylon.
On the other hand, the improvement in spinning process mainly contain following aspect: (1) reduces the aperture of spinning jet, and as using the diameter 0.2mm even the spinning jet of fine pore more, and the hole of corresponding increase spinning jet is long; (2) filter to improve the purity of spinning melt by high precision; (3) reduce spray silk level of stretch and degree of molecular orientation of tow in the winding process and extend abilities with more reservation tow; (4) take higher drafting multiple.
The nylon fiber fabric is best suited for one of man-made fabric of human dress.Therefore, the nylon fiber monofilament carried out the thin dawn or super fine denierization extremely important, and select suitable spinning material very important beyond doubt for producing thin dawn or superfine denier nylon fibre.
, with regard to mentioned prior art, all can't be reasonably with thin dawn of nylon fiber or super fine denierization, the fiber number of gained fiber is generally still at least greater than 1.0dtex.
In addition, the contriver develops a kind of master batch auxiliary agent before this, this master batch auxiliary agent is to be formed by metallic compound and nylon matrix thorough mixing melt-processed, utilizes this master batch auxiliary agent and nylon particle to carry out direct scorification spinning, can reach the purpose of spinning denier/superfine denier nylon long filament.Correlation technique has been applied for patent, and detailed technology information is to elaborate in the patent documentations such as CN101122053A, CN101139750A, CN101311389A, CN101724265A at publication number.
Summary of the invention
Deficiency at above-mentioned prior art existence, the object of the present invention is to provide a kind of Nylon 66 that is used for producing thin dawn or super fine denier nylon 66 long filaments, and carry out melt-spinning by this resin and produce thin dawn or super fine denier nylon 66 long filaments of fiber number less than 1.0dtex.
Another object of the present invention is to provide a kind of preparation method who produces thin dawn or super fine denier nylon 66 long filaments.
The objective of the invention is to be implemented by the following technical programs:
The present invention at first provides a kind of Nylon 66, and it is by the compound of nylon salt melt and rare earth metal after polymerization and aftercondensated reaction make, and wherein, based on the weight meter of nylon salt, the weight of the compound of rare earth metal is 0.01～0.8%.
Major technique design of the present invention is, by in the nylon salt melt, adding a kind of compound of rare earth metal, (be polymerization+aftercondensated reaction through specific chain condensation polymerization technology after being uniformly dispersed, be the continuous condensed technology of transverse tube type) obtain can be used in and produce the resin dedicated of thin dawn or super fine denier nylon 66 long filaments, this is resin dedicated to have extraordinary performance, for example can directly be spun into thin dawn or super fine denier nylon 66 long filaments by method of the present invention.
Discover, the affiliation that adds of the compound of rare earth metal makes nylon 66 melts show good performance in the melt-spinning process, for example high strength, high viscosity, high tensile deformation and high spinning property etc., thus make Nylon 66 of the present invention can be spun into thin dawn or super fine denier nylon 66 long filaments of fiber number less than 1.0dtex.Can be spun into the effect of thin dawn or superfine denier nylon fibre in order to ensure Nylon 66, the usage quantity of the compound of rare earth metal is as follows: based on the weight meter of used nylon salt, the compound weight of rare earth metal is 0.01～0.8wt%, be preferably 0.1%～0.6wt%, most preferably be 0.2～0.4wt%.If the usage quantity of the compound of rare earth metal is lower than 0.01wt%, then its modified effect to Nylon 66 is good inadequately, causes special-purpose nylon 66 resins to be difficult to be spun into thin dawn or super fine denier nylon 66 long filaments; If the usage quantity of the compound of rare earth metal is greater than 0.8wt%, then the amount of the compound of the rare earth metal of Tian Jiaing is too much, makes that resin dedicated molecular weight distribution is irregular, the metallic compound particle is easily reunited, stop up orifice, cause the spinning effect variation, filametntary quality is variation thereupon.
As preferably, according to a kind of Nylon 66 of the present invention, wherein, the compound of described rare earth metal is the salt or the complex compound of rare earth metal, wherein, described rare earth metal is selected from lanthanum, cerium, yttrium or europium etc., and it is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand or polynary part that the negatively charged ion of the salt of described rare earth metal or the part of complex compound are selected from hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, acetate moiety, sulfonate radical, inferior sulfate radical, thiosulfate anion, halide anion, pseudohalogen ion and other.The examples for compounds indefiniteness of described rare earth metal comprises: Phosbloc, cerous carbonate, yttrium carbonate, europium carbonate; Lanthanum orthophosphate, Cerium monophosphate, yttrium phosphate, phosphoric acid europium; Lanthanum acetate, cerous acetate, acetic acid yttrium, acetic acid europium; Lanthanum sulfat, cerous sulfate, yttrium sulfate, europium sulfate; Sulfonic acid lanthanum, cerous iodate, sulfonic acid yttrium, sulfonic acid europium; Lanthanum trichloride, Cerium II Chloride, Yttrium trichloride, Europium trichloride etc.
As preferably, according to a kind of Nylon 66 of the present invention, wherein, add initiator, molecular weight stabilizer and softening agent in the described polyreaction, wherein, described initiator is meant distilled water or deionized water, and the addition of initiator accounts for 0.5～2.0% of nylon salt weight; Described molecular weight stabilizer is meant acetic acid or/and hexanodioic acid, and the addition of molecular weight stabilizer accounts for 0.1～1.0% of nylon salt weight; Described softening agent is meant hexanolactam, and the addition of softening agent accounts for 1.0～5.0% of nylon salt weight.The polymerization of Nylon 66 of the present invention mainly causes the nylon salt condensation polymerization by initiator, is aided with the regulation and control that molecular weight stabilizer and softening agent carry out the fluoropolymer resin molecular weight.
As preferably, according to a kind of Nylon 66 of the present invention, wherein, because polymerization process is in comparatively high temps all the time, between 240-290 ℃, in order to guarantee polymer material unlikely oxidative degradation under the condition of high temperature, do not reduce the viscosity of polymer material, do not influence the back spinning properties, also add heat-resisting stabilizing agent in the described polyreaction, based on the weight meter of nylon salt, described heat-resisting stabilizing agent is selected from more than one in the following substances: H320/H321 series 0.1-0.4%, Magnesium Stearate 0.02-0.07% and neutralized verdigris 0.02-0.07%.Heat-resisting stabilizing agent H320/H321 series belongs to the compound of cupric iodide-potassiumiodide, is the commercially available prod.
As preferably, according to a kind of Nylon 66 of the present invention, wherein, and in the described polyreaction: the method that main employing progressively heats, polymerization temperature control divides four-stage, and material temperature before entering Gao Yiguan is controlled between 210 ~ 225 ℃; Entered by Gao Yiguan in the transverse tube process at material, polymerization takes place, and the moisture of generation evaporates in a large number, needs constantly heating, and temperature of charge is maintained between 235 ~ 265 ℃; After entering the Senior Two pipe, temperature is controlled between 260 ~ 280 ℃, and drop temperature is controlled between 250-275 ℃; Material successively passes through drawdown pump, flash distillation pump and deaerator afterwards, removes the bubble in the material, and controlled temperature is between 270 ~ 290 ℃; Polymerization pressure is the 10-20 kg/cm, and the dwell time is 60-180min.Polymerization temperature control has decisive role for the quality of Nylon 66 product.By control pressure size and polymerization dwell time, reach the purpose of the resin that obtains suitable molecular weight and distribution.
It is a kind of by nylon 66 long filaments of above-mentioned Nylon 66 through the melt spinning method preparation that the present invention also provides.Nylon 66 of the present invention adopts direct melt spinning method, can produce thin dawn or super fine denier nylon 66 long filaments on common high-speed spinning equipment, and the intensity of fiber and elongation at break all meet the back requirements of weaving process.
As preferably, according to nylon 66 long filaments of the present invention, wherein, the fiber number of described nylon 66 long filaments is 0.1～1.0dtex.Optimize the performance quality of nylon 66, can enlarge its range of application.
The present invention also provides the preparation method of above-mentioned nylon 66 long filaments, comprise: Nylon 66 is carried out melt-spinning, and wherein, in the melt-spinning process: the temperature of nylon 66 molten masses is between 180～320 ℃, preferably between 240-290 ℃, most preferably between 260-285 ℃; The hole count of spinning jet is 10～120, and the aperture is 0.1～0.7mm, and the spinning jet length-to-diameter ratio is 2.0～4.0; The speed of reeling is 2000～5500m/min.The reason of each parameter is with reference to conventional nylon spinning parameter in the control melt spinning method, in conjunction with the performance of denier/superfine denier nylon fiber, and corresponding changing.For example, single fiber is thin, need reduce orifice diameter, thereby reduces the spinneret draft multiple, and tow is not ruptured; The resin that contains metal-salt, the corresponding increase of melt viscosity for improving fluidity of molten, needs correspondingly heighten spinning temperature 5-10 ℃ etc.
As preferably, according to the preparation method of nylon 66 long filaments of the present invention, wherein, before the described melt-spinning Nylon 66 is carried out drying, to remove moisture and small-molecule substance, drying temperature is 90-100 ℃, be 24-48 hour time of drying.
Preparation method of the present invention, operation is simple, be convenient to operation, can obtain thin dawn or super fine denier nylon 66 long filaments of fiber number less than 1.0dtex, and in preparation process, nylon 66 long filament tow can not rupture basically, and the mechanical property of thin dawn of gained or super fine denier nylon 66 long filaments is fine, and fiber number is minimum can to reach about 0.1dtex.
As preferably, according to the preparation method of nylon 66 long filaments of the present invention, wherein, also carry out hot drawing-off before the described coiling, the temperature of hot drawing-off is between 90-200 ℃.Controlling hot drawing temperature is to make temperature be higher than the second-order transition temperature of nylon fiber in the reason of this scope, so that fiber segment sufficient movement, orientation degree, the degree of order increase; But when temperature was too high, fiber was easy to fusing, and strength degradation makes the tow fracture.The advantage that increases hot this operation of drawing-off is to increase fiber segment motor capacity, and the fibre orientation degree is increased, and degree of crystallinity improves, thereby the intensity of fortifying fibre in addition, also can suitably reduce the fiber number of fiber, obtains the littler fiber of filament number.
Term " fiber number " is used for representing the thickness degree of nylon fiber herein, represents with " dtex " usually." dtex " is the unit of fiber number, and 1dtex is meant that the fiber quality of long 10000m is 1 gram.
Term " melt spinning method " is meant the raw material heating and melting that spinning is used herein, molten mass is delivered to spinning-drawing machine after extruding by screw extrusion press, quantitatively be pressed into molten mass in the spinning components through volume pump, by the orifice on the spinning jet nylon 66 melts are extruded with the filament attitude, the moulding of cross air blow postcooling, obtain finished product through oil boundling and coiling again, also through overheated drawing-off, promptly get thin dawn or super fine denier nylon 66 long filaments behind the boundling that perhaps oils.
Term " melt-spinning process " comprises from former and expects all processes that become silk herein, for example the melting process that will carry out preprocessing process that raw material that spinning uses carries out, raw material and molten mass is become the silk process.
The word of the expression scope of Chu Xianing herein, as " less than ", " greater than " and " ... in the scope " etc., its represented scope comprises the endpoint value of respective range.
The compound that adds rare earth metal can obviously improve the spinning property and the weaving security of nylon 66, thereby can obtain thin dawn or super fine denier nylon 66 long filaments of fiber number less than 1.0dtex.The contriver thinks that possible mechanism is as follows: the compound of rare earth metal can with nylon 66 molecule generation complex coordination effects, change the melt structure of nylon, improve the intensity of nylon 66 melts, improve the viscosity of molten mass, reduce melt flow index MFI, thereby make it can bear bigger drawing force, even when nylon 66 melts become the fritting body behind the spray silk, still have tensile strength preferably, therefore can tolerate bigger drawing force, the tension force that makes fibre bundle in the melt-spinning process, can bear in the drawing-down step to be born and can not rupturing, thereby improve the spinning property of nylon, obtain thin dawn or super fine denier nylon 66 long filaments.But effect of the present invention is not subjected to the constraint of this theory.
The present invention compared with prior art has the following advantages:
1. the present invention adopts and add properties-correcting agent metallic salt material in the nylon salt melt, initiated polymerization after this, thus treat to make after polymerization is finished resin dedicated.Metallic salt can change nylon 66 melt structures, and the tensile strength of Reinforced Nylon 66 melts reduces the crystallization rate of nylon 66 melts simultaneously, thereby a kind of denier/superfine denier brocade nylon 66 long filaments of can producing on common high-speed spinning equipment are provided; The resulting ultra-fine fibre of the present invention can be contained plurality of specifications, has stable excellent properties, weaves the different demands of arrangement processing after can satisfying, the ultra-fine fibre kind of the present invention's exploitation, also can produce non-woven, medical, filtering material etc. enlarges its range of application;
2. the present invention adopts and adds in earlier stage in polymerization, guarantee metallic compound homodisperse in nylon 66 matrixes, and give full play of metal-salt and nylon 66 intermolecular interactions strengthening the modification ability, thereby make special-purpose resin and spin denier/superfine denier nylon 66 long filaments.
3. the present invention adopts and adds metallic compound before the polymerization, not only with the island method, peel off composite spinning method such as method and compare, technology is simple, cost reduces, and is a kind of eco-friendly high-performance fiber production technology; And utilize the master batch method to produce denier/superfine denier nylon 6 long filament technology before this with the contriver and compare, in this in-situ polymerization technology, metallic compound is dispersed better in nylon 66 matrixes, modifying function is more obvious, and technology is simplified more, reduced the influence of spinning technique flow process to fibre property, made the gained fibre property stable, quality is more excellent; Simultaneously also reduce energy consumption, met the policy and the requirement of energy-saving and emission-reduction.
4. use resin dedicated and production method of the present invention can obtain thin dawn or super fine denier nylon 66 long filaments that fiber number is about 0.10～1.0dtex, the intensity of this fiber and elongation at break all meet the back requirements of weaving process.Fill up the blank that domestic denier/superfine denier nylon 66 long filaments adopt conventional high speed spinning method to produce, promoted the scientific and technological content and the added value of nylon 66 continuous yarn products.
Description of drawings
Fig. 1 is Nylon 66 production technique of the present invention (the continuous condensed technology of a transverse tube type) schematic flow sheet.
Fig. 2 is the technological process of production synoptic diagram of nylon 66 long filaments of the present invention.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all equipment and raw material etc. all can be buied from market or the industry is commonly used.Method among the following embodiment if no special instructions, is the ordinary method of this area.
Main raw material:
Nylon salt: the refreshing horse engineering plastics in tafelberg limited liability company.
Embodiment 1
As shown in Figure 1: above-mentioned materials and distilled water are mixed (temperature is controlled at about 95 ℃) in storage barrel, the concentration of aqueous solution of nylon salt is maintained about 60%.Constantly above-mentioned material is sent in the preheater by ram pump, after being preheated to 212 ℃, enter among the Gao Yiguan, and constantly be pushed into a horizontal pipe and horizontal two pipes, Gao Yiguan enters in the transverse tube process, make material maintain 235-245 ℃, material is pushed in the Senior Two pipe then, after material enters the Senior Two pipe, temperature is controlled between 260-270 ℃, and steam is discharged through vapor pipe by a large amount of evaporations in the material; Nylon salt concentration increases, beginning polycondensation (temperature remains on 260-265 ℃); Polymer melt successively enters (temperature maintenance is at 270-275 ℃) in flasher, the deaerator through drawdown pump, and wherein, polymerization pressure is 10kg/cm
2, the dwell time is 1 hour.After removing residual moisture, polymer melt enters further polymerization in the final polycondensation reactor, about polymerization time 30min, by the discharging screw rod product is extruded through the Cast Strip pelletizing again, again through vacuum-drying, drying temperature is at 90 ℃, be 48 hours time of drying, promptly gets Nylon 66 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 66 that obtains is carried out melt-spinning, molten mass is delivered to spinning-drawing machine after extruding by screw extrusion press, quantitatively be pressed into molten mass in the spinning components through volume pump, by the orifice on the spinning jet nylon 66 melts are extruded with the filament attitude, again through cross air blow, cooling forming, oil boundling, hot drawing-off and coiling obtains fine denier nylon 66 long filament finished products, wherein, the temperature of molten mass in screw extrusion press Zhong Ge district is respectively 260 ℃, 268 ℃, 268 ℃, 273 ℃, and spinning temperature is 272 ℃; 90 ℃ of hot drafting forming temperature, the The hole diameter of spinneret that adopts is 0.35mm, length is 0.7mm, hole count is 10 holes, winding speed is 2000m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is fine denier nylon 66 long filaments of 0.9dtex, Mechanics Performance Testing intensity reaches 4.0cN/dtex, and elongation at break is 110%.
Experiment shows, with the LaCl in the table 1
3Cl
-It is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand or polynary part to replace to hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, acetate, sulfonate radical, inferior sulfate radical, thiosulfate anion, other halide anions, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 2
As shown in Figure 1: above-mentioned materials and distilled water are mixed (temperature is controlled at about 95 ℃) in storage barrel, the concentration of aqueous solution of nylon salt is maintained about 60%.Constantly above-mentioned material is sent in the preheater by ram pump, after being preheated to 213 ℃, enter among the Gao Yiguan, and constantly be pushed into a horizontal pipe and horizontal two pipes, Gao Yiguan enters in the transverse tube process, make material maintain 238-243 ℃, material is pushed in the Senior Two pipe then, after material enters the Senior Two pipe, temperature is controlled between 260-265 ℃, and steam is discharged through vapor pipe by a large amount of evaporations in the material; Nylon salt concentration increases, beginning polycondensation (temperature remains on 263-268 ℃); Polymer melt successively enters (temperature maintenance is at 273-276 ℃) in flasher, the deaerator through drawdown pump, and wherein, polymerization pressure is 12kg/cm
2, the dwell time is 1.5 hours.After removing residual moisture, polymer melt enters further polymerization in the final polycondensation reactor, about polymerization time 90min, by the discharging screw rod product is extruded through the Cast Strip pelletizing again, again through vacuum-drying, drying temperature is at 90 ℃, be 30 hours time of drying, promptly gets Nylon 66 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 66 that obtains is carried out melt-spinning, molten mass is delivered to spinning-drawing machine after extruding by screw extrusion press, quantitatively be pressed into molten mass in the spinning components through volume pump, by the orifice on the spinning jet nylon 66 melts are extruded with the filament attitude, again through cross air blow, cooling forming, oil boundling, hot drawing-off and coiling obtains super fine denier nylon 66 long filament finished products, wherein, the temperature of molten mass in screw extrusion press Zhong Ge district is respectively 262 ℃, 270 ℃, 270 ℃, 275 ℃, and spinning temperature is 275 ℃; 120 ℃ of hot drafting forming temperature, the The hole diameter of spinneret that adopts is 0.25mm, length is 0.7mm, hole count is 24 holes, winding speed is 3000m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is fine denier nylon 66 long filaments of 0.8dtex, Mechanics Performance Testing intensity reaches 4.2cN/dtex, and elongation at break is 100%.
Experiment shows, with the Yi in the table 2
2(SO
4)
3SO
4 2-It is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand or polynary part to replace to hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, acetate, sulfonate radical, inferior sulfate radical, thiosulfate anion, halide anion, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 3
As shown in Figure 1: above-mentioned materials and distilled water are mixed (temperature is controlled at about 95 ℃) in storage barrel, the concentration of aqueous solution of nylon salt is maintained about 60%.Constantly above-mentioned material is sent in the preheater by ram pump, after being preheated to 215 ℃, enter among the Gao Yiguan, and constantly be pushed into a horizontal pipe and horizontal two pipes, Gao Yiguan enters in the transverse tube process, make material maintain 240-245 ℃, material is pushed in the Senior Two pipe then, after material enters the Senior Two pipe, temperature is controlled between 263-268 ℃, and steam is discharged through vapor pipe by a large amount of evaporations in the material; Nylon salt concentration increases, beginning polycondensation (temperature remains on 265-270 ℃); Polymer melt successively enters (temperature maintenance is at 275-278 ℃) in flasher, the deaerator through drawdown pump, and wherein, polymerization pressure is 14kg/cm
2, the dwell time is 2 hours.After removing residual moisture, polymer melt enters further polymerization in the final polycondensation reactor, about polymerization time 45min, by the discharging screw rod product is extruded through the Cast Strip pelletizing again, again through vacuum-drying, drying temperature is at 96 ℃, be 36 hours time of drying, promptly gets Nylon 66 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 66 that obtains is carried out melt-spinning, molten mass is delivered to spinning-drawing machine after extruding by screw extrusion press, quantitatively be pressed into molten mass in the spinning components through volume pump, by the orifice on the spinning jet nylon 66 melts are extruded with the filament attitude, again through cross air blow, cooling forming, oil boundling, hot drawing-off and coiling obtains super fine denier nylon 66 long filament finished products, wherein, the temperature of molten mass in screw extrusion press Zhong Ge district is respectively 265 ℃, 275 ℃, 275 ℃, 280 ℃, and spinning temperature is 278 ℃; 140 ℃ of hot drafting forming temperature, the The hole diameter of spinneret that adopts is 0.20mm, length is 0.6mm, hole count is 48 holes, winding speed is 4000m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is fine denier nylon 66 long filaments of 0.6dtex, Mechanics Performance Testing intensity reaches 5.1 cN/dtex, and elongation at break is 55%.
Experiment shows, with the Eu in the table 3 (Ac)
3Ac
-It is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand or polynary part to replace to hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, sulfonate radical, inferior sulfate radical, thiosulfate anion, halide anion, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 4
As shown in Figure 1: above-mentioned materials and distilled water are mixed (temperature is controlled at about 95 ℃) in storage barrel, the concentration of aqueous solution of nylon salt is maintained about 60%.Constantly above-mentioned material is sent in the preheater by ram pump, after being preheated to 225 ℃, enter among the Gao Yiguan, and constantly be pushed into a horizontal pipe and horizontal two pipes, Gao Yiguan enters in the transverse tube process, make material maintain 255-265 ℃, material is pushed in the Senior Two pipe then, after material enters the Senior Two pipe, temperature is controlled between 275-280 ℃, and steam is discharged through vapor pipe by a large amount of evaporations in the material; Nylon salt concentration increases, beginning polycondensation (temperature remains on 270-275 ℃); Polymer melt successively enters (temperature maintenance is at 280-285 ℃) in flasher, the deaerator through drawdown pump, and wherein, polymerization pressure is 20kg/cm
2, the dwell time is 3 hours.After removing residual moisture, polymer melt enters further polymerization in the final polycondensation reactor, about polymerization time 60min, by the discharging screw rod product is extruded through the Cast Strip pelletizing again, again through vacuum-drying, drying temperature is at 95 ℃, be 48 hours time of drying, promptly gets Nylon 66 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 66 that obtains is carried out melt-spinning, molten mass is delivered to spinning-drawing machine after extruding by screw extrusion press, quantitatively be pressed into molten mass in the spinning components through volume pump, by the orifice on the spinning jet nylon 66 melts are extruded with the filament attitude, again through cross air blow, cooling forming, oil boundling, hot drawing-off and coiling obtains super fine denier nylon 66 long filament finished products, wherein, the temperature of molten mass in screw extrusion press Zhong Ge district is respectively 270 ℃, 290 ℃, 290 ℃, 288 ℃, and spinning temperature is 285 ℃; 200 ℃ of hot drafting forming temperature, the The hole diameter of spinneret that adopts is 0.15mm, length is 0.60mm, hole count is 72 holes, winding speed is 4800m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is super fine denier nylon 66 long filaments of 0.3dtex, Mechanics Performance Testing intensity reaches 5.6cN/dtex, and elongation at break is 38%.
Experiment shows, with the Ce in the table 4
3(S
2SO
3)
4S
2SO
3 2-It is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand or polynary part to replace to hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, acetate, sulfonate radical, inferior sulfate radical, halide anion, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 5
As shown in Figure 1: above-mentioned materials and distilled water are mixed (temperature is controlled at about 95 ℃) in storage barrel, the concentration of aqueous solution of nylon salt is maintained about 60%.Constantly above-mentioned material is sent in the preheater by ram pump, after being preheated to 223 ℃, enter among the Gao Yiguan, and constantly be pushed into a horizontal pipe and horizontal two pipes, Gao Yiguan enters in the transverse tube process, make material maintain 255-260 ℃, material is pushed in the Senior Two pipe then, after material enters the Senior Two pipe, temperature is controlled between 270-275 ℃, and steam is discharged through vapor pipe by a large amount of evaporations in the material; Nylon salt concentration increases, beginning polycondensation (temperature remains on 268-273 ℃); Polymer melt successively enters (temperature maintenance is at 278-282 ℃) in flasher, the deaerator through drawdown pump, and wherein, polymerization pressure is 18kg/cm
2, the dwell time is 3 hours.After removing residual moisture, polymer melt enters further polymerization in the final polycondensation reactor, about polymerization time 90min, by the discharging screw rod product is extruded through the Cast Strip pelletizing again, again through vacuum-drying, drying temperature is at 95 ℃, be 48 hours time of drying, promptly gets Nylon 66 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 66 that obtains is carried out melt-spinning, molten mass is delivered to spinning-drawing machine after extruding by screw extrusion press, quantitatively be pressed into molten mass in the spinning components through volume pump, by the orifice on the spinning jet nylon 66 melts are extruded with the filament attitude, again through cross air blow, cooling forming, oil boundling, hot drawing-off and coiling obtains super fine denier nylon 66 long filament finished products, wherein, the temperature of molten mass in screw extrusion press Zhong Ge district is respectively 270 ℃, 285 ℃, 285 ℃, 288 ℃, and spinning temperature is 283 ℃; 180 ℃ of hot drafting forming temperature, the The hole diameter of spinneret that adopts is 0.12mm, length is 0.48mm, hole count is 120 holes, winding speed is 5500m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is super fine denier nylon 66 long filaments of 0.1dtex, Mechanics Performance Testing intensity reaches 5.8cN/dtex, and elongation at break is 33%.
Experiment shows, with the LaCl in the table 5
3Cl
-It is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand or polynary part to replace to phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, acetate, sulfonate radical, inferior sulfate radical, thiosulfate anion, other halide anions, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water, can realize same technique effect, gives unnecessary details no longer one by one herein.
Above preferred embodiment just is used for description and interpretation content of the present invention, does not constitute the restriction to content of the present invention.Although the contriver has done in more detail the present invention and has enumerated, but, the content that those skilled in the art is disclosed according to summary of the invention part and embodiment, can make various modifications or/and to replenish or adopt similar mode to substitute be obvious to described specific embodiment, and can realize technique effect of the present invention, therefore, give unnecessary details no longer one by one herein.The term that occurs among the present invention is used for the elaboration of technical solution of the present invention and understanding are not construed as limiting the invention.
Claims (10)
1. Nylon 66, it is characterized in that described Nylon 66 is by the compound of nylon salt melt and rare earth metal after polymerization and aftercondensated reaction make, wherein, based on the weight meter of nylon salt, the weight of the compound of rare earth metal is 0.01～0.8%.
2. a kind of Nylon 66 according to claim 1, it is characterized in that, the compound of described rare earth metal is the salt or the complex compound of rare earth metal, wherein, described rare earth metal is selected from lanthanum, cerium, yttrium or europium, and it is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand or polynary part that the negatively charged ion of the salt of described rare earth metal or the part of complex compound are selected from hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, acetate moiety, sulfonate radical, inferior sulfate radical, thiosulfate anion, halide anion, pseudohalogen ion and other.
3. a kind of Nylon 66 according to claim 1, it is characterized in that, add initiator, molecular weight stabilizer and softening agent in the described polyreaction, wherein, described initiator is meant distilled water or deionized water, and the addition of initiator accounts for 0.5～2.0% of nylon salt weight; Described molecular weight stabilizer is meant acetic acid or/and hexanodioic acid, and the addition of molecular weight stabilizer accounts for 0.1～1.0% of nylon salt weight; Described softening agent is meant hexanolactam, and the addition of softening agent accounts for 1.0～5.0% of nylon salt weight.
4. a kind of Nylon 66 according to claim 3, it is characterized in that, also add heat-resisting stabilizing agent in the described polyreaction, based on the weight meter of nylon salt, described heat-resisting stabilizing agent is selected from more than one in the following substances: H320/H321 series 0.1-0.4%, Magnesium Stearate 0.02-0.07% and neutralized verdigris 0.02-0.07%.
5. a kind of Nylon 66 according to claim 1 is characterized in that, in the described polyreaction: the method that main employing progressively heats, polymerization temperature control divides four-stage, and material temperature before entering Gao Yiguan is controlled between 210 ~ 225 ℃; Enter in the transverse tube process by Gao Yiguan at material, temperature of charge is maintained between 235 ~ 265 ℃; After entering the Senior Two pipe, temperature is controlled between 260 ~ 280 ℃, makes drop temperature be controlled at 250-275 ℃; Material successively passes through drawdown pump, flash distillation pump and deaerator afterwards, and controlled temperature is between 270 ~ 290 ℃; Polymerization pressure is the 10-20 kg/cm, and the dwell time is 60-180min.
6. one kind by nylon 66 long filaments of the arbitrary described Nylon 66 of claim 1-5 through melt spinning method preparation.
7. nylon 66 long filaments according to claim 6 is characterized in that the fiber number of described nylon 66 long filaments is 0.1～1.0dtex.
8. the preparation method of nylon 66 long filaments as claimed in claim 6 is characterized in that, described preparation method comprises: Nylon 66 is carried out melt-spinning, and wherein, in the melt-spinning process: the temperature of nylon 66 molten masses is between 180～320 ℃; The hole count of spinning jet is 10～120, and the aperture is 0.1～0.7mm, and the spinning jet length-to-diameter ratio is 2.0～4.0; The speed of reeling is 2000～5500m/min.
9. the preparation method of nylon 66 long filaments according to claim 8 is characterized in that, before the described melt-spinning Nylon 66 is carried out drying, and drying temperature is 90-100 ℃, and be 24-48 hour time of drying.
10. the preparation method of nylon 66 long filaments according to claim 8 is characterized in that, also carries out hot drawing-off before the described coiling, and the temperature of hot drawing-off is between 90-200 ℃.
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| CN104562275A (en) * | 2014-11-27 | 2015-04-29 | 杭州师范大学 | Porous micro-fine denier nylon 6 POY filament yarns and preparation method thereof |
| CN110273196A (en) * | 2018-10-21 | 2019-09-24 | 杭州师范大学 | A kind of temperature adjustment long filament and preparation method thereof |
| CN114527234A (en) * | 2022-01-14 | 2022-05-24 | 神马实业股份有限公司 | Method for testing carboxyl content in nylon 66 polymer |
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