CN102199283A - Nylon 6 resin, nylon 6 filament and preparation methods thereof - Google Patents
Nylon 6 resin, nylon 6 filament and preparation methods thereof Download PDFInfo
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Abstract
The invention relates to the field of spinning materials and provides a nylon 6 resin. The nylon 6 resin is prepared by carrying out polymerization reaction on a mixing fusant of a caprolactam monomer and a rare-earth metal compound, wherein the weight percentage of the rare-earth metal compound is 0.01-0.8% on the basis of the total weight of the caprolactam monomer. The invention also provides a nylon 6 filament made of the nylon 6 resin, and the nylon 6 filament is obtained by carrying out melt spinning on the nylon 6 resin. Fine denier or super-fine denier nylon filaments with fineness of about 0.20-1.0dtex can be obtained by using the nylon 6 resin and the preparation method thereof; the strength and the elongation at break of the fiber are in line with post-weaving requirements, the blank that the fine denier or super-fine denier nylon 6 filaments can be manufactured by adopting a conventional high-speed spinning method at home and abroad is filled up, and the technological content and the additional value of a nylon 6 fiber product are increased.
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 6 of producing thin dawn or super fine denier nylon 6 long filaments, nylon 6 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 and nylon, polypropylene fibre, terylene and acrylic fibers etc. by spinning processing, 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 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.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 about 3-6dtex), 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 the technical scheme and the strict control spinning of choose reasonable spinning, every production process such as drawing-off.
Yet up to the present, the research report that improves the 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, as using the diameter 0.2mm even the spinning jet of fine pore more, and the hole count of corresponding increase spinning jet; (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 it is very important beyond doubt for producing thin dawn or superfine denier nylon fibre to choose suitable spinning material.
, 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 6 that is used for producing thin dawn or super fine denier nylon 6 long filaments, and carry out melt-spinning by this resin and produce thin dawn or super fine denier nylon 6 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 6 long filaments.
The objective of the invention is to be implemented by the following technical programs:
A kind of Nylon 6 is that the blend melt by the compound of caprolactam monomer and rare earth metal makes through polyreaction, and wherein, based on caprolactam monomer gross weight meter, the weight of the compound of rare earth metal is 0.01～0.8%.
Major technique design of the present invention is, by in caprolactam monomer, adding a kind of compound of rare earth metal, the compound of an amount of rare earth metal directly is dissolved in the hexanolactam melt, obtain to produce the resin dedicated of thin dawn or super fine denier nylon 6 long filaments by the ring opening agent initiated polymerization again after being uniformly dispersed, described resin dedicated main component is the nylon-6 matrix body that is polymerized by caprolactam monomer, this is resin dedicated to have extraordinary performance, for example can directly be spun into thin dawn or superfine denier nylon fibre by method of the present invention.
Discover, the affiliation that adds of the compound of rare earth metal makes nylon 6 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 6 of the present invention can be spun into thin dawn or super fine denier nylon 6 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 6, the usage quantity of the compound of rare earth metal is as follows: based on used caprolactam monomer gross weight meter, the compound weight of rare earth metal is 0.01～0.8wt%, be preferably 0.1%～0.7wt%, more preferably 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 is good inadequately, causes the special-purpose nylon resin to be difficult to be spun into thin dawn or superfine denier nylon fibre; 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, make that resin dedicated molecular weight distribution is irregular, simultaneously, the rare earth compound particle is easily assembled, and disperses irregularly in nylon matrix, easily stops up orifice, cause the spinning effect variation, quality of fiber is variation thereupon.
As preferably, according to a kind of Nylon 6 of the present invention, wherein, the compound of described rare earth metal is rare earth metal salt or complex compound, wherein, described rare earth metal is selected from lanthanum, cerium, yttrium or europium, it is nitrogenous and/or contain oxygen (as carboxylate radical) and/or sulfur-bearing organic ligand or polynary part that the negatively charged ion of described rare earth metal salt 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, halide anion, pseudohalogen ion (for example, thiocyanate ion) and other.Particularly, 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 6 of the present invention, wherein, add ring opening agent and molecular weight stabilizer in the described polyreaction, wherein, described ring opening agent is meant distilled water or deionized water, and the addition of ring opening agent accounts for 0.8～4% of caprolactam monomer gross weight, is preferably 2～4%; Described molecular weight stabilizer is meant acetic acid or/and hexanodioic acid, and the addition of molecular weight stabilizer accounts for 0.1～0.5% of caprolactam monomer gross weight, is preferably 0.2～0.4%.The polymerization of Nylon 6 of the present invention mainly causes the caprolactam monomer polymerization by ring opening agent, is aided with the regulation and control that molecular weight stabilizer carries out the fluoropolymer resin molecular weight.
As preferably, according to a kind of Nylon 6 of the present invention, wherein, in the described polyreaction: temperature control divides three phases, material is at the straight type successive polymerization of normal pressure pipe (being called for short straight type VK pipe) epimere, and temperature is controlled between 250～300 ℃, is preferably 250～275 ℃, be beneficial to heat up caprolactam monomer open loop and draining; In the straight type successive polymerization of normal pressure pipe stage casing, temperature is controlled between 235～270 ℃, is preferably 245～265 ℃, is beneficial to the growth of molecular chain; At the straight type successive polymerization of normal pressure pipe hypomere, temperature is controlled between 220～260 ℃, is preferably 230～255 ℃, is beneficial to the raising of resin molecular-weight average and the content of low-molecular material.By temperature and the polymerization time (being generally 10-20hr) of controlling straight type VK pipe, obtain the purpose of the resin of suitable molecular weight and molecular weight distribution with realization.
It is a kind of by nylon 6 long filaments of above-mentioned Nylon 6 through the melt spinning method preparation that the present invention also provides.Nylon 6 of the present invention adopts direct melt spinning method, can produce thin dawn or super fine denier nylon 6 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 6 long filaments of the present invention, wherein, the fiber number of described nylon 6 long filaments is 0.2～1.0dtex.Optimize the performance quality of nylon 6, can enlarge its range of application.
The present invention also provides a kind of preparation method of above-mentioned nylon 6 long filaments, comprise: Nylon 6 is carried out melt-spinning, wherein, in the melt-spinning process: the temperature of nylon 6 molten masses is between 130～320 ℃, more preferably in 180～280 ℃ of scopes, most preferably in 250～275 ℃ of scopes; The hole count of spinning jet is 10～100, and the aperture is 0.1～0.8mm, 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 6 long filaments of the present invention, wherein, before the described melt-spinning Nylon 6 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 6 long filaments of fiber number less than 1.0dtex, and in preparation process, nylon 6 long filament tow can not rupture basically, and the mechanical property of thin dawn of gained or super fine denier nylon 6 long filaments is fine, and fiber number is minimum can to reach about 0.2dtex.
As preferably, according to the preparation method of nylon 6 long filaments of the present invention, wherein, also do hot drawing-off before the described coiling, the temperature of hot drawing-off is between 50-170 ℃.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 6 melts are extruded with the filament attitude, the cross air blow cooling forming, obtain finished product through oil boundling and coiling again, also through overheated drafting forming, and then coiling and molding promptly gets thin dawn or super fine denier nylon 6 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 6, thereby can obtain thin dawn or super fine denier nylon 6 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 6 molecule generation complex coordination effects, change the melt structure of nylon, improve the intensity of nylon 6 melts, improve the viscosity of molten mass, reduce melt flow index MFI, thereby make it can bear bigger drawing force, even when nylon 6 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 step to be born and can not rupturing, thereby improve the spinning property of nylon, obtain thin dawn or super fine denier nylon 6 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 before the caprolactam monomer polymerization, thereby makes special-purpose nylon 6 resins after polymerization is finished.Metallic salt can change nylon 6 melt structures, the tensile strength of while Reinforced Nylon 6 melts, and the crystallization rate of reduction nylon 6 melts can be produced denier/superfine denier nylon 6 long filaments thereby provide a kind of on common high-speed spinning equipment; 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 the nylon-6 matrix body, and give full play of metal-salt and the intermolecular interaction of nylon strengthening the modification ability, thereby make resin dedicated and spin denier/superfine denier nylon 6 long filaments.
3. the present invention adopts and adds metal salt 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, metal salt compound is good dispersity in nylon matrix, modifying function is more obvious, and technology is simplified more, reduced of the influence of spinning technique flow process to fibre property, make 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 special-purpose nylon 6 resins of the present invention and production method can obtain thin dawn or super fine denier nylon 6 long filaments that fiber number is about 0.20～1.0dtex, 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 6 long filaments adopt conventional high speed spinning method to produce, promoted the scientific and technological content and the added value of nylon 6 continuous yarn products.
Description of drawings
Fig. 1 is a Nylon 6 technological process of production synoptic diagram of the present invention.
Fig. 2 is the technological process of production synoptic diagram of nylon 6 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:
Caprolactam monomer: Yueyang Ba Ling petrochemical industry company limited produces.
Embodiment 1
As shown in Figure 1: above-mentioned materials is mixed in storage barrel, constantly above-mentioned material is sent in the straight type VK pipe by fresh feed pump, material is by the ring opening agent initiated polymerization, temperature control divides three phases in the described polyreaction, material is at straight type VK pipe epimere, and temperature is controlled between 250～260 ℃; Straight type VK pipe stage casing, temperature is controlled between 235～245 ℃; Straight type VK pipe hypomere, temperature is controlled between 230～235 ℃, and polymer melt is taken out of it by discharging pump through flowing to VK pipe bottom under the baffle plate layer by layer, and with liquid level in the holding tube, polymerization time is 10 hours.With the resulting polymers melt through the washing pelletizing, through vacuum-drying, to remove moisture and small-molecule substance.Drying temperature is at 90 ℃, and be 24 hours time of drying, promptly gets Nylon 6 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 6 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 6 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 6 long filament finished products, wherein, melt screw extrusion press Zhong Ge district temperature be respectively 250 ℃, 255 ℃, 255 ℃, 260 ℃, spinning temperature is 253 ℃; 50 ℃ of hot drafting forming temperature, the spinning jet hole count of employing is 10, and the aperture is 0.30mm, and length is 0.8mm; Winding speed is 2000m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is fine denier nylon 6 long filaments of 0.9dtex, and Mechanics Performance Testing intensity reaches 3.3cN/dtex, and elongation at break is 120%.
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, other halide anions, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water; Hexanodioic acid replaces to the mixture of acetic acid or acetic acid and hexanodioic acid arbitrary proportion, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 2
As shown in Figure 1: above-mentioned materials is mixed in storage barrel, constantly above-mentioned material is sent in the straight type VK pipe by fresh feed pump, material is by the ring opening agent initiated polymerization, temperature control divides three phases in the described polyreaction, material is at straight type VK pipe epimere, and temperature is controlled at temperature and is controlled between 255～265 ℃; Straight type VK pipe stage casing, temperature is controlled between 240～250 ℃; Straight type VK pipe hypomere, temperature is controlled between 235～240 ℃, and polymer melt is taken out of it by discharging pump through flowing to VK pipe bottom under the baffle plate layer by layer, and with liquid level in the holding tube, polymerization time is 14 hours.With the resulting polymers melt through the washing pelletizing, through vacuum-drying, to remove moisture and small-molecule substance.Drying temperature is at 100 ℃, and be 30 hours time of drying, promptly gets Nylon 6 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 6 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 6 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 6 long filament finished products, wherein, melt screw extrusion press Zhong Ge district temperature be respectively 250 ℃, 260 ℃, 260 ℃, 263 ℃, spinning temperature is 257 ℃; 90 ℃ of hot drafting forming temperature, the spinning jet hole count of employing is 24, and the aperture is 0.3mm, and length is 0.6mm; Winding speed is 3000m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is fine denier nylon 6 long filaments of 0.8dtex, and Mechanics Performance Testing intensity reaches 3.7cN/dtex, elongation at break 98%.
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, nitrate 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; Hexanodioic acid replaces to the mixture of acetic acid or acetic acid and hexanodioic acid arbitrary proportion, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 3
As shown in Figure 1: above-mentioned materials is mixed in storage barrel, constantly above-mentioned material is sent in the straight type VK pipe by fresh feed pump, material is by the ring opening agent initiated polymerization, temperature control divides three phases in the described polyreaction, material is at straight type VK pipe epimere, and temperature is controlled between 260～268 ℃; Straight type VK pipe stage casing, temperature is controlled between 243～253 ℃; Straight type VK pipe hypomere, temperature is controlled between 238～248 ℃, and polymer melt is taken out of it by discharging pump through flowing to VK pipe bottom under the baffle plate layer by layer, and with liquid level in the holding tube, polymerization time is 18 hours.With the resulting polymers melt through the washing pelletizing, through vacuum-drying, to remove moisture and small-molecule substance.Drying temperature is at 95 ℃, and be 36 hours time of drying, promptly gets Nylon 6 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 6 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 6 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 6 long filament finished products, wherein, melt screw extrusion press Zhong Ge district temperature be respectively 252 ℃, 262 ℃, 262 ℃, 265 ℃, spinning temperature is 260 ℃; 120 ℃ of hot drafting forming temperature, the spinning jet hole count of employing is 48, and the aperture is 0.25mm, and length is 0.6mm; Winding speed is 4000m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is super fine denier nylon 6 long filaments of 0.6dtex, and Mechanics Performance Testing intensity reaches 4.2cN/dtex, elongation at break 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, halide anion, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water; Hexanodioic acid replaces to the mixture of acetic acid or acetic acid and hexanodioic acid arbitrary proportion, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 4
As shown in Figure 1: above-mentioned materials is mixed in storage barrel, constantly above-mentioned material is sent in the straight type VK pipe by fresh feed pump, material is by the ring opening agent initiated polymerization, temperature control divides three phases in the described polyreaction, material is at straight type VK pipe epimere, and temperature is controlled between 265～275 ℃; Straight type VK pipe stage casing, temperature is controlled between 260～270 ℃; Straight type VK pipe hypomere, temperature is controlled between 245～255 ℃, and polymer melt is taken out of it by discharging pump through flowing to VK pipe bottom under the baffle plate layer by layer, and with liquid level in the holding tube, polymerization time is 18 hours.With the resulting polymers melt through the washing pelletizing, through vacuum-drying, to remove moisture and small-molecule substance.Drying temperature is at 95 ℃, and be 48 hours time of drying, promptly gets Nylon 6 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 6 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 6 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 6 long filament finished products, wherein, melt screw extrusion press Zhong Ge district temperature be respectively 260 ℃, 275 ℃, 275 ℃, 278 ℃, spinning temperature is 275 ℃; 170 ℃ of hot drafting forming temperature, the spinning jet hole count of employing is 72, and the aperture is 0.15mm, and length is 0.6mm; Winding speed is 4000m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is super fine denier nylon 6 long filaments of 0.5dtex, and Mechanics Performance Testing intensity reaches 4.3cN/dtex, elongation at break 45%.
Experiment shows, with the Eu in the table 4 (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, halide anion, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water; Hexanodioic acid replaces to the mixture of acetic acid or acetic acid and hexanodioic acid arbitrary proportion, can realize same technique effect, gives unnecessary details no longer one by one herein.
Embodiment 5
As shown in Figure 1: above-mentioned materials is mixed in storage barrel, constantly above-mentioned material is sent in the straight type VK pipe by fresh feed pump, material is by the ring opening agent initiated polymerization, temperature control divides three phases in the described polyreaction, material is at straight type VK pipe epimere, and temperature is controlled between 260～270 ℃; Straight type VK pipe stage casing, temperature is controlled between 260～265 ℃; Straight type VK pipe hypomere, temperature is controlled between 245～250 ℃, and polymer melt is taken out of it by discharging pump through flowing to VK pipe bottom under the baffle plate layer by layer, and with liquid level in the holding tube, polymerization time is 20 hours.With the resulting polymers melt through the washing pelletizing, through vacuum-drying, to remove moisture and small-molecule substance.Drying temperature is at 90 ℃, and be 48 hours time of drying, promptly gets Nylon 6 of the present invention.
As shown in Figure 2: then the above-mentioned Nylon 6 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 6 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 6 long filament finished products, wherein, melt screw extrusion press Zhong Ge district temperature be respectively 260 ℃, 273 ℃, 273 ℃, 275 ℃, spinning temperature is 273 ℃; 160 ℃ of hot drafting forming temperature, the spinning jet hole count of employing is 100, and the aperture is 0.35mm, and length is 0.7mm; Winding speed is 5500m/min, and by adjusting the volume pump rotating speed, obtaining the undrawn yarn fiber number is super fine denier nylon 6 long filaments of 0.20dtex, and Mechanics Performance Testing intensity reaches 5.0cN/dtex, and elongation at break is 35%.
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 hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, acetate, sulfonate radical, inferior sulfate radical, other halide anions, pseudohalogen ion and other, as porphyrin, thiocyanate ion, alanine root etc.; Distilled water replaces to deionized water; Hexanodioic acid replaces to the mixture of acetic acid or acetic acid and hexanodioic acid arbitrary proportion, 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 (9)
1. Nylon 6, it is characterized in that described Nylon 6 is that the blend melt by the compound of caprolactam monomer and rare earth metal makes through polyreaction, wherein, based on caprolactam monomer gross weight meter, the weight of the compound of rare earth metal is 0.01～0.8%.
2. a kind of Nylon 6 according to claim 1, it is characterized in that, the compound of described rare earth metal is rare earth metal salt or complex compound, 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 described rare earth metal salt or the part of complex compound are selected from hydroxide radical, phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, acetate, sulfonate radical, inferior sulfate radical, halide anion, pseudohalogen ion and other.
3. a kind of Nylon 6 according to claim 1, it is characterized in that, add ring opening agent and molecular weight stabilizer in the described polyreaction, wherein, described ring opening agent is meant distilled water or deionized water, and the addition of ring opening agent accounts for 0.8～4% of caprolactam monomer gross weight; Described molecular weight stabilizer is meant acetic acid or/and hexanodioic acid, and the addition of molecular weight stabilizer accounts for 0.1～0.5% of caprolactam monomer gross weight.
4. a kind of Nylon 6 according to claim 1 is characterized in that, in the described polyreaction: temperature control divides three phases, and material is at the straight type successive polymerization of normal pressure pipe epimere, and temperature is controlled between 250～300 ℃; In the straight type successive polymerization of normal pressure pipe stage casing, temperature is controlled between 235～270 ℃; At the straight type successive polymerization of normal pressure pipe hypomere, temperature is controlled between 220～260 ℃; Polymerization time is 10-20h.
5. one kind by nylon 6 long filaments of the arbitrary described Nylon 6 of claim 1～4 through melt spinning method preparation.
6. nylon 6 long filaments according to claim 5 is characterized in that the fiber number of described nylon 6 long filaments is 0.2～1.0dtex.
7. the preparation method of nylon 6 long filaments as claimed in claim 5 is characterized in that, described preparation method comprises: Nylon 6 is carried out melt-spinning, and wherein, in the melt-spinning process: the temperature of nylon 6 molten masses is between 130～320 ℃; The hole count of spinning jet is 10～100, and the aperture is 0.1～0.8mm, and the spinning jet length-to-diameter ratio is 2.0～4.0; The speed of reeling is 2000～5500m/min.
8. the preparation method of nylon 6 long filaments according to claim 7 is characterized in that, before the described melt-spinning Nylon 6 is carried out drying, and drying temperature is 90-100 ℃, and be 24～48 hours time of drying.
9. the preparation method of nylon 6 long filaments according to claim 7 is characterized in that, also does hot drawing-off before the described coiling, and the temperature of hot drawing-off is between 50～170 ℃.
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| CN102775767A (en) * | 2012-05-21 | 2012-11-14 | 宁波泛龙塑料新材料有限公司 | High-heat-conduction nylon composite material and preparation method thereof |
| CN103571173A (en) * | 2012-07-19 | 2014-02-12 | 中国科学院化学研究所 | Modified polymer and preparation method thereof |
| CN104060343A (en) * | 2013-03-19 | 2014-09-24 | 浙江美丝邦化纤有限公司 | Fine-denier and super-fine-denier chinlon 6 fibers and manufacturing method thereof |
| CN104562250A (en) * | 2014-11-27 | 2015-04-29 | 杭州师范大学 | Micro-porous fine denier nylon 6 three-difference fiber and preparation method and application thereof |
| 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 |
| CN105440280A (en) * | 2015-07-20 | 2016-03-30 | 杭州师范大学 | Preparation method and application of anti-radiation nylon 6 resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102775767A (en) * | 2012-05-21 | 2012-11-14 | 宁波泛龙塑料新材料有限公司 | High-heat-conduction nylon composite material and preparation method thereof |
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| CN104060343A (en) * | 2013-03-19 | 2014-09-24 | 浙江美丝邦化纤有限公司 | Fine-denier and super-fine-denier chinlon 6 fibers and manufacturing method thereof |
| CN104060343B (en) * | 2013-03-19 | 2016-08-31 | 浙江美丝邦化纤有限公司 | Fine-denier and super fine denier nylon-6 fiber and manufacture method thereof |
| CN104562250A (en) * | 2014-11-27 | 2015-04-29 | 杭州师范大学 | Micro-porous fine denier nylon 6 three-difference fiber and preparation method and application thereof |
| 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 |
| CN105440280A (en) * | 2015-07-20 | 2016-03-30 | 杭州师范大学 | Preparation method and application of anti-radiation nylon 6 resin |
| CN105440280B (en) * | 2015-07-20 | 2018-05-29 | 杭州师范大学 | A kind of preparation method of radiation protection nylon 6 resin and application |
| CN113265716A (en) * | 2021-05-17 | 2021-08-17 | 福建师范大学泉港石化研究院 | Polyamide fiber with anti-ultraviolet performance and preparation method thereof |
| CN113265716B (en) * | 2021-05-17 | 2022-03-22 | 福建师范大学泉港石化研究院 | Polyamide fiber with anti-ultraviolet performance and preparation method thereof |
| WO2022241979A1 (en) * | 2021-05-17 | 2022-11-24 | 福建师范大学泉港石化研究院 | Polyamide fiber having anti-ultraviolet performance and preparation method therefor |
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