A two-stage method and device for preparing cross-linked fibers

Abstract

The present invention provides a method for preparing crosslinked fibers by a two-stage method, comprising: treating fiber ribbons with a crosslinking agent solution and a catalyst solution respectively, and then curing the fiber ribbons to obtain crosslinked fibers. Compared with the prior art, the present invention not only avoids the hydrolysis and self-polymerization of the crosslinking agent under the action of the catalyst, thereby improving the crosslinking effect, but also reduces the influence of the catalytic bath on the crosslinking agent impregnated onto the fiber ribbons, thereby improving the stability of the crosslinked product and reducing the production cost. The present invention also provides a device for preparing crosslinked fibers by a two-stage method.

Description

Technical Field

[0001] The invention belongs to the technical field of cross-linked fibers, and in particular relates to a method and a device for preparing cross-linked fibers by a two-stage process. Background Art

[0002] Traditional TAHT cross-linked fibers (such as Figure 1 The preparation device shown in the figure) is to mix the crosslinking agent and the catalyst in a certain proportion for use. In this method, although the crosslinking agent has activity under the action of the catalyst, the activated crosslinking agent is prone to hydrolysis and flocculation, reacts prematurely, and loses its activity. This will result in a reduction in the crosslinking effect, a waste of crosslinking agent and an increase in production costs. In the existing equipment process, when the crosslinking temperature is 80°C, when 0.92%wt TAHT (1,3,5-triacryloylhexahydro-1,3,5-triazine) and 0.2%wt NaOH are prepared, the crosslinking agent hydrolysis rate reaches 11.04g / (L*h), which means that the original crosslinking agent will be completely hydrolyzed within 50 minutes. In production, in order to achieve the stability of the crosslinking effect, it is necessary to continuously add crosslinking agents and catalysts to the crosslinking bath. With the market price of TAHT being 110,000 / t and the crosslinking agent storage tank being 3m 3 It is calculated that the annual cost of cross-linking agent hydrolysis is about 31.914 million yuan. Summary of the invention

[0003] In view of this, the object of the present invention is to provide a two-stage method and device for preparing cross-linked fibers. The method provided by the present invention can prevent the cross-linking agent from being hydrolyzed and self-polymerized under the action of a catalyst during the preparation of the cross-linked fibers.

[0004] The present invention provides a two-stage method for preparing crosslinked fibers, comprising:

[0005] The fiber ribbons are treated with a crosslinking agent solution and a catalyst solution respectively, and then cured to obtain crosslinked fibers.

[0006] Preferably, the method of treating the cross-linking agent solution is padding or spraying;

[0007] The catalyst solution is treated by padding or spraying.

[0008] Preferably, the two-stage method for preparing crosslinked fibers specifically comprises:

[0009] The fiber ribbon is dipped in a crosslinking agent solution and then dried, and then dipped in a catalyst solution and then cured to obtain a crosslinked fiber; or

[0010] The fiber ribbon is dipped in a catalyst solution and then dried, and then dipped in a crosslinking agent solution and then cured to obtain a crosslinked fiber.

[0011] Preferably, the two-stage method for preparing crosslinked fibers specifically comprises:

[0012] The fiber ribbon is dipped in a crosslinking agent solution and then sprayed with a catalyst solution, and then cured to obtain a crosslinked fiber; or

[0013] The fiber ribbon is dipped in a catalyst solution and then sprayed with a crosslinking agent solution, and then cured to obtain a crosslinked fiber.

[0014] Preferably, during the spraying process, the spray liquid is sprayed on the fiber ribbon transported from bottom to top, and the spray liquid flows downward along the fiber ribbon.

[0015] Preferably, before the spraying, the method further comprises:

[0016] The fiber ribbon is divided into at least two fiber sub-ribbons.

[0017] Preferably, the crosslinker in the crosslinker solution is selected from 1,3,5-triacryloylhexahydro-1,3,5-triazine (TAHT), the catalyst in the catalyst solution is selected from one or more of sodium hydroxide, trisodium phosphate and sodium carbonate, and the mass ratio of the fiber ribbon, the crosslinker in the crosslinker solution and the catalyst in the catalyst solution is 100:(0.1-7):(0.1-13).

[0018] Preferably, the crosslinker in the crosslinker solution is selected from methylated hexahydroxymethylmelamine resin (HMMM), the catalyst in the catalyst solution is selected from one or more of methanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfone, and the mass ratio of the fiber ribbon, the crosslinker in the crosslinker solution and the catalyst in the catalyst solution is 100: (0.1-10): (0.6-8).

[0019] Preferably, it also includes:

[0020] adding sodium sulfate to the cross-linking agent solution;

[0021] The mass ratio of the fiber ribbon to sodium sulfate is 100:(1-13).

[0022] The present invention provides a device for preparing cross-linked fibers by a two-stage process, comprising:

[0023] Cross-linking agent solution processing equipment;

[0024] a catalyst solution processing device connected to the cross-linking agent solution processing device;

[0025] A curing device, wherein the inlet of the curing device is connected to the outlet of the cross-linking agent solution processing device or the outlet of the catalyst solution processing device;

[0026] A water washing tank whose inlet is connected to the outlet of the curing equipment.

[0027] Compared with the prior art, the present invention avoids the hydrolysis and self-polymerization of the crosslinking agent under the action of the catalyst, thereby improving the crosslinking effect; it also reduces the influence of the catalytic bath on the crosslinking agent impregnated onto the fiber, thereby improving the stability of the crosslinked product and reducing the production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic diagram of the structure of a device for preparing cross-linked fibers in the prior art;

[0029] Figure 2 A schematic diagram of the structure of an apparatus for preparing cross-linked fibers provided in Example 1 of the present invention;

[0030] Figure 3 This is a schematic diagram of the structure of the spray chamber in Example 1 of the present invention;

[0031] Figure 4 This is a schematic diagram of the structure of the device for preparing cross-linked fibers provided in Example 2 of the present invention. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other examples improved or modified by ordinary technicians in this field belong to the scope of protection of the present invention. It should be understood that the embodiments of the present invention are only used to illustrate the technical effects of the present invention, rather than to limit the scope of protection of the present invention. In the embodiments, the methods used are conventional methods unless otherwise specified.

[0033] The present invention provides a two-stage method for preparing crosslinked fibers, comprising:

[0034] The fiber ribbons are treated with a crosslinking agent solution and a catalyst solution respectively, and then cured to obtain crosslinked fibers.

[0035] In the present invention, the method for treating with the crosslinking agent solution is preferably padding or spraying; the method for treating with the curing agent solution is preferably dipping or spraying.

[0036] In the present invention, the two-stage method for preparing crosslinked fibers preferably comprises:

[0037] The fiber ribbon is dipped in a crosslinking agent solution and then dried, and then dipped in a catalyst solution and then cured to obtain a crosslinked fiber; or

[0038] The fiber ribbon is dipped in a catalyst solution and then dried, and then dipped in a crosslinking agent solution and then cured to obtain a crosslinked fiber.

[0039] In the present invention, drying is performed between immersion in the crosslinking agent solution and immersion in the catalyst solution, which is beneficial to reduce the desorption rate of the crosslinking agent during immersion in the catalyst solution and improve the crosslinking effect. In the present invention, the drying temperature is preferably 65°C to 90°C, more preferably 70°C to 85°C, and most preferably 75°C to 80°C.

[0040] In the present invention, the two-stage method for preparing crosslinked fibers preferably comprises:

[0041] The fiber ribbon is dipped in a crosslinking agent solution and then sprayed with a catalyst solution, and then cured to obtain a crosslinked fiber; or

[0042] The fiber ribbon is dipped in a catalyst solution and then sprayed with a crosslinking agent solution, and then cured to obtain a crosslinked fiber.

[0043] In the present invention, the cross-linked fiber prepared by immersing the fiber ribbon in a catalyst solution and then spraying the cross-linking agent solution has a better cross-linking effect.

[0044] In the present invention, the two-stage method of padding and spraying is preferably used to prepare the cross-linked fiber, which can reduce the hydrolysis of the cross-linking agent and thus reduce the preparation cost of the cross-linked fiber.

[0045] In the present invention, the spraying liquid (crosslinking agent solution or catalyst solution) is preferably sprayed on the fiber ribbon transported from bottom to top during the spraying process, so that the spraying liquid moves naturally downward along the fiber ribbon. In the present invention, the fiber ribbon is preferably arranged vertically to improve the utilization rate of the spraying liquid.

[0046] In the present invention, the spraying preferably further comprises:

[0047] The fiber ribbon after spraying is subjected to extrusion treatment;

[0048] During the process between spraying and squeezing, the fiber ribbon moves from bottom to top in a direction parallel to the fiber ribbon, so that the squeezed liquid (crosslinking agent solution or catalyst solution) naturally flows downward along the fiber ribbon.

[0049] In the present invention, the best arrangement of the fiber ribbons during the process of spraying and extrusion is vertical arrangement, which can ensure that the extruded liquid flows smoothly downward along the fiber ribbons. However, the arrangement of the fiber ribbons in the present invention is not limited to this. The fiber ribbons can also have a certain inclination angle according to actual process requirements, as long as the extruded liquid (cross-linking agent solution or catalyst solution) can still flow on the fiber ribbons and does not drip from the fiber ribbons.

[0050] In the present invention, the spraying process is preferably arranged below the extrusion process. When the fiber ribbon after spraying enters the extrusion process, it is preferably transported from the spraying process from bottom to top to the extrusion process in a direction parallel to the fiber ribbon. When the fiber ribbon is extruded, the liquid (cross-linking agent solution or catalyst solution) squeezed out naturally flows downward along the fiber ribbon. Since the squeezed liquid (cross-linking agent solution or catalyst solution) naturally flows downward along the fiber ribbon under the action of gravity, the liquid (cross-linking agent solution or catalyst solution) and the fiber ribbon can be more fully and evenly fitted, and the liquid (cross-linking agent solution or catalyst solution) is promoted to be evenly immersed in the gaps of the fiber ribbon; and the liquid (cross-linking agent solution or catalyst solution) squeezed out by the extrusion roller re-participates in the immersion cross-linking of the fiber ribbon, further improving the utilization rate of the cross-linking liquid.

[0051] In the present invention, the spraying preferably further comprises:

[0052] The fiber ribbon is divided into at least two fiber sub-ribbons.

[0053] In the present invention, each fiber sub-ribbon has two sides; during the spraying process, the liquid (cross-linking agent solution or catalyst solution) is evenly sprayed on both sides of each fiber sub-ribbon.

[0054] In the present invention, the fiber ribbon is preferably divided into at least three fiber sub-ribbons, each fiber sub-ribbon has two sides, and during the spraying process, the two sides of each fiber sub-ribbon are preferably evenly sprayed with the spray liquid (cross-linking agent solution or catalyst solution). In the present invention, the fiber ribbon is divided into more than two sub-ribbons, and each sub-ribbon is sprayed with the spray liquid, so that the fiber ribbon is more fully in contact with the spray liquid.

[0055] In the present invention, before the extrusion, a plurality of fiber sub-ribbons are preferably gathered to form a fiber ribbon and then extruded.

[0056] The present invention can further improve the impregnation effect of the liquid (crosslinker solution or catalyst solution) and the fiber ribbon through the above operation. First, the fiber ribbon is divided into two or more sub-ribbons, and each sub-ribbon is sprayed with liquid (crosslinker solution or catalyst solution) to make the fiber ribbon and the liquid (crosslinker solution or catalyst solution) contact more fully; secondly, the sub-ribbons are gathered into a set of rollers for squeezing to form a fiber ribbon. In this way, at the moment of squeezing, the liquid (crosslinker solution or catalyst solution) penetrates from the inside and outside of the fiber ribbon at the same time, thereby improving the fiber impregnation effect; thirdly, this can reduce the amount of liquid (crosslinker solution or catalyst solution) sprayed on the surface of each sub-ribbon, so that a relatively thin crosslinking liquid layer is formed on the surface of the sub-ribbon, and unexpectedly reduces the adverse effect of the catalyst on the crosslinker.

[0057] In the present invention, during the spraying process, it is preferred that the sprayed liquid (crosslinker solution or catalyst solution) penetrates the fiber ribbon horizontally and is sprayed on both sides of the fiber ribbon, or on both sides of each fiber sub-ribbon, so that the liquid (crosslinker solution or catalyst solution) can be sprayed more evenly on the fiber ribbon.

[0058] The present invention has no special restrictions on the method of the extrusion treatment, and the fiber ribbon can be extruded by using an extrusion roller using an extrusion method well known to those skilled in the art. In the present invention, the extrusion treatment adjusts the rolling ratio by adjusting the pressure of the extrusion roller, and the rolling ratio is preferably 100% to 180%.

[0059] In the present invention, the padding temperature is preferably 60 to 90°C, more preferably 65 to 85°C, more preferably 70 to 80°C, and most preferably 75°C.

[0060] In the present invention, the padding is preferably performed multiple times, more preferably 1 to 4 times, and most preferably 2 to 3 times.

[0061] In the present invention, the rolling ratio of the impregnation is preferably 90 to 150%, more preferably 100 to 140%, more preferably 110 to 130%, and most preferably 120%.

[0062] In the present invention, the fiber ribbon is preferably a lyocell fiber ribbon.

[0063] In the present invention, the temperature of the cross-linking agent solution is preferably 60-90°C, more preferably 65-85°C, more preferably 70-80°C, and most preferably 75°C.

[0064] In the present invention, when the crosslinker in the crosslinker solution is preferably selected from 1,3,5-triacryloylhexahydro-1,3,5-triazine, the catalyst in the catalyst solution is preferably selected from one or more of sodium hydroxide, trisodium phosphate and sodium carbonate; preferably, it also includes: adding sodium sulfate to the crosslinker solution; the mass ratio of the fiber ribbon and sodium sulfate is preferably 100: (1-13), more preferably 100: (3-10), more preferably 100: (5-8), and most preferably 100: (6-7); the mass ratio of the fiber ribbon, the crosslinker in the crosslinker solution and the catalyst in the catalyst solution is preferably 100: (0.1-7): (0.1-13), more preferably 100: (0.5-6): (0.5-10), more preferably 100: (1-5): (1-8), more preferably 100: (2-4): (3-6), and most preferably 100: 3: (4-5).

[0065] In the present invention, when the crosslinker in the crosslinker solution is preferably selected from methylated hexahydroxymethylmelamine resin, the catalyst in the catalyst solution is preferably selected from one or more of methanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfone, and the mass ratio of the fiber ribbon, the crosslinker in the crosslinker solution and the catalyst in the catalyst solution is preferably 100:(0.1-10):(0.6-8), more preferably 100:(0.5-8):(1-7), more preferably 100:(1-6):(2-6), more preferably 100:(2-5):(3-5), and most preferably 100:(3-4):4.

[0066] In the present invention, the mass ratio of the crosslinking agent solution (preferably TAHT solution) to the fiber ribbon is preferably (0.109-1.087):1, more preferably (0.326-0.761):1, and most preferably 0.543:1.

[0067] In the present invention, when the fiber ribbon is dipped in a crosslinker solution, the crosslinker in the crosslinker solution is preferably TAHT (1,3,5-triacryloylhexahydro-1,3,5-triazine); the mass concentration of TAHT in the crosslinker solution is preferably 0.1-10%, more preferably 0.5-8%, more preferably 1-6%, more preferably 2-5%, and most preferably 3-4%; in the present invention, when the crosslinker solution is used to spray the fiber ribbon, the crosslinker in the crosslinker solution is preferably TAHT; the mass concentration of the crosslinker solution is preferably 0.1-10%, more preferably 0.5-8%, more preferably 1-6%, more preferably 2-5%, and most preferably 3-4%.

[0068] In the present invention, the concentration of the catalyst solution is preferably 0.01-5%wt, more preferably 0.05%-4%wt, more preferably 0.1-3%wt, more preferably 0.5-2.5%wt, more preferably 1-2%wt, and most preferably 1.5%wt.

[0069] In the present invention, the solvent in the cross-linking agent solution is preferably selected from water; the solvent in the catalyst solution is preferably selected from water.

[0070] In the present invention, the curing temperature is preferably 80 to 160°C, more preferably 90 to 150°C, more preferably 100 to 140°C, more preferably 110 to 130°C, and most preferably 120°C.

[0071] In the present invention, the curing time is preferably 10 to 60 min, more preferably 20 to 50 min, more preferably 30 to 40 min, and most preferably 35 min.

[0072] In the present invention, after the curing is completed, it is preferred to include:

[0073] The solidified product is washed with water and dried to obtain lyocell fibers with antigen fibrillation ability.

[0074] In the present invention, the drying temperature is preferably 65-90°C, more preferably 70-85°C, most preferably 75-80°C.

[0075] Compared with the prior art, the present invention avoids the hydrolysis and self-polymerization of the crosslinking agent under the action of the catalyst, thereby improving the crosslinking effect; it also reduces the influence of the catalytic bath on the crosslinking agent impregnated onto the fiber, thereby improving the stability of the crosslinked product and reducing the production cost.

[0076] The present invention provides a device for preparing cross-linked fibers by a two-stage process, comprising:

[0077] Cross-linking agent solution processing equipment;

[0078] a catalyst solution processing device connected to the cross-linking agent solution processing device;

[0079] A curing device, wherein the inlet of the curing device is connected to the outlet of the cross-linking agent solution processing device or the outlet of the catalyst solution processing device;

[0080] A water washing tank connected to the outlet of the curing equipment.

[0081] In the present invention, the crosslinking agent solution treatment equipment is preferably a padding tank or a spray chamber; the catalyst solution treatment equipment is preferably a padding tank or a spray chamber. In the present invention, the two-stage method for preparing crosslinked fibers preferably includes:

[0082] First padding tank;

[0083] A drying device having an inlet connected to an outlet of the first padding tank;

[0084] a second padding tank having an inlet connected to an outlet of the drying device;

[0085] a curing device having an inlet connected to an outlet of the second padding tank;

[0086] A water washing tank whose inlet is connected to the outlet of the curing equipment.

[0087] In the present invention, the first padding pool can be a cross-linking agent padding pool or a catalyst padding pool, and the first padding pool can be filled with a cross-linking agent solution or a catalyst solution; the second padding pool can be a cross-linking agent padding pool or a catalyst padding pool, and the second padding pool can be filled with a cross-linking agent solution or a catalyst solution; the padding liquids in the first padding pool and the second padding pool are different.

[0088] In the present invention, the device for preparing crosslinked fibers by the two-stage method preferably comprises:

[0089] padding tank;

[0090] a spray chamber having an inlet connected to an outlet of the padding tank;

[0091] a curing device having an inlet connected to an outlet of the spray chamber;

[0092] A water washing tank whose inlet is connected to the outlet of the curing equipment.

[0093] In the present invention, the padding pool may contain a crosslinking agent solution or a catalyst solution; the spray liquid in the spray chamber may be a crosslinking agent solution or a catalyst solution; the padding liquid in the padding pool is different from the spray liquid in the spray chamber.

[0094] In the present invention, the device for preparing crosslinked fibers by the two-stage method preferably comprises:

[0095] Spray room;

[0096] a padding tank having an inlet connected to an outlet of the spray chamber;

[0097] a curing device having an inlet connected to an outlet of the padding tank;

[0098] A water washing tank whose inlet is connected to the outlet of the curing equipment.

[0099] In the present invention, the spray liquid in the spray chamber can be either a crosslinker solution or a catalyst solution; the padding liquid in the padding pool can be either a crosslinker solution or a catalyst solution, and the spray liquid in the spray chamber is different from the padding liquid in the padding pool.

[0100] The present invention has no special limitation on the first padding pool, the second padding pool and the padding pool. Any padding pool well known to those skilled in the art can be used as long as the fiber ribbon can be padded.

[0101] The present invention has no special limitation on the drying equipment. Any drying equipment known to those skilled in the art can be used to dry the fiber ribbon after padding.

[0102] The present invention has no special limitation on the curing device, and any curing device well known to those skilled in the art can be used to perform curing treatment on the fiber ribbon.

[0103] The present invention has no special limitation on the water washing tank, and a water washing tank well known to those skilled in the art can be used to wash the fiber ribbon.

[0104] In the present invention, the padding pool and the spray chamber are preferably connected via rollers to transport the padded fiber ribbons into the spray chamber.

[0105] In the present invention, the spray chamber is preferably arranged vertically so that the fiber ribbon between the bottom and the top of the spray chamber is transported from bottom to top in the vertical direction during the spraying process.

[0106] In the present invention, a distribution assembly is preferably provided at the bottom end of the spray chamber so that the fiber ribbon is distributed into at least two fiber sub-ribbons before spraying; the distribution assembly is preferably a roller, more preferably a group of rollers, and the distribution assembly can be formed by several pairs of rollers.

[0107] In the present invention, rollers are arranged from the bottom to the top of the spray chamber, which are used to transport the fiber ribbons from bottom to top and to converge and squeeze the fiber ribbons through the rollers at the top; the rollers are preferably multiple.

[0108] In the present invention, the spray chamber is preferably further provided with a temperature control system for adjusting the temperature in the spray chamber. The present invention has no particular limitation on the temperature control system, and a temperature control device well known to those skilled in the art can be used to control the temperature in the spray chamber. In the present invention, the temperature control system is preferably an electric heating wire, such as a heating wire can be wound inside the spray chamber; the temperature control system is preferably a jacket, such as a jacket can be designed for the spray chamber to control the temperature by passing steam into the jacket.

[0109] In the present invention, a cavity, a high-pressure pipe and a nozzle are provided in the spray chamber, the cavity is used to place the spray liquid (cross-linking agent solution or catalyst solution), the outlet of the cavity is connected to the inlet of the high-pressure pipe, and the outlet of the high-pressure pipe is connected to the inlet of the nozzle. In the present invention, the spray liquid in the cavity is transported to the nozzle through the high-pressure pipe and sprayed from the nozzle onto the fiber ribbon. In the present invention, a plurality of nozzles are preferably provided in the spray chamber; the nozzles are provided on both sides of the fiber ribbon or the fiber sub-ribbon, and nozzles are provided on both sides of each fiber ribbon or the fiber sub-ribbon. In the present invention, the nozzle of the nozzle is preferably flat, and the length of the nozzle is preferably consistent with the width of the fiber ribbon or the fiber sub-ribbon, which is conducive to the uniform spraying of the cross-linking liquid on the fiber ribbon.

[0110] In the present invention, the structural schematic diagram of the spray chamber is as follows Figure 3 As shown, the spray chamber is vertically arranged, including: a cavity 8, a high-pressure pipe 10 connected to the cavity outlet, a nozzle 11 connected to the high-pressure pipe outlet, and a plurality of rollers 12 are arranged from the bottom to the top of the spray chamber shell 9, which are used to first distribute the fiber ribbon in the spray chamber into at least two fiber sub-ribbons, and transport them from bottom to top to the top, and gather the sprayed fiber sub-ribbons into one fiber ribbon at the top roller and extrude them; the nozzles are arranged on both sides of the fiber sub-ribbons in the middle of the spray chamber shell.

[0111] In the present invention, the spray chamber and the curing device are preferably connected via rollers to transport the sprayed fiber ribbons to the curing device for curing.

[0112] Compared with the prior art, the present invention avoids the hydrolysis and self-polymerization of the crosslinking agent under the action of the catalyst, thereby improving the crosslinking effect; it also reduces the influence of the catalytic bath on the crosslinking agent impregnated onto the fiber, thereby improving the stability of the crosslinked product and reducing the production cost.

[0113] The test method of the wet wear value (WAV) in the following embodiments of the present invention is: the nominal linear density D and the number of wet wear circles N of 20 fibers to be tested are simultaneously tested using Lenzing instruments' VIBROSKOP 500 fineness meter and DELTA 100 wet wear meter. The larger the wet wear value, the stronger the fiber's ability to resist fibrillation. The calculation formula of the wet wear value WAV (unit: r / dtex) is shown as follows:

[0114]

[0115] Example 1

[0116] This embodiment provides a structure such as Figure 2 The device for preparing cross-linked fibers shown comprises:

[0117] Padding tank 4;

[0118] A spray chamber 5 having an inlet connected to the outlet of the padding tank;

[0119] A curing device 6 having an inlet connected to an outlet of the spray chamber;

[0120] A water washing tank 7 whose inlet is connected to the outlet of the curing device;

[0121] The spray room is set vertically. The structural diagram of the spray room is as follows: Figure 3 As shown, it includes: a cavity 8, a spray chamber shell 9, a high-pressure pipeline 10, a nozzle 11, and a roller 12;

[0122] The cavity is used to place the spray liquid (cross-linking agent solution or catalyst solution), the outlet of the cavity is connected to the inlet of the high-pressure pipeline, and the outlet of the high-pressure pipeline is connected to the inlet of the nozzle; the spray liquid in the cavity is transported to the nozzle through the high-pressure pipeline and sprayed to the fiber sub-ribbon; the nozzle is multiple and arranged on both sides of the fiber sub-ribbon in the middle of the spray chamber shell, the nozzle orifice is flat, and the length of the nozzle is the same as the width of the fiber sub-ribbon;

[0123] A plurality of rollers are arranged from the bottom to the top of the spray chamber shell, which are used to divide the fiber ribbon entering the spray chamber into at least two fiber sub-ribbons, transport the fiber ribbon from bottom to top, and gather and squeeze the fiber sub-ribbons after spraying; an electric heating wire is wound inside the spray chamber as a temperature control system to control the temperature of the spray chamber;

[0124] The fiber ribbon after extrusion enters the curing equipment for curing and then is washed in a water washing tank to obtain cross-linked fibers;

[0125] The padding pool and the spraying chamber are connected by rollers, and the padded fiber ribbons are transported to the spraying chamber for spraying;

[0126] The spray chamber and the curing equipment are connected by rollers, and the fiber ribbons after spraying are transported to the curing equipment for curing;

[0127] The curing equipment and the washing tank are connected by rollers, and the cured fiber ribbons are transported to the washing tank for washing.

[0128] Example 2

[0129] This embodiment provides a structure such as Figure 4 The device for preparing cross-linked fibers shown comprises:

[0130] Cross-linking agent padding tank 13;

[0131] A drying device 14 having an inlet connected to an outlet of the crosslinking agent padding tank;

[0132] A catalyst padding tank 15 whose inlet is connected to the outlet of the drying equipment;

[0133] A curing device 16 having an inlet connected to an outlet of the catalyst padding tank;

[0134] A water washing tank 17 whose inlet is connected to the outlet of the curing device;

[0135] The cross-linking agent padding tank, the drying equipment, the catalyst padding tank, the curing equipment and the washing tank are connected by rollers, so that the fiber ribbons are sequentially transported to the cross-linking agent padding tank to be dipped in the cross-linking agent solution, dried in the drying equipment, dipped in the catalyst padding tank to be dipped in the catalyst solution, cured in the curing equipment, and washed in the washing tank.

[0136] Example 3

[0137] The cross-linked fiber is prepared using the cross-linked fiber preparation device provided in Example 1:

[0138] At 80°C, the lyocell fiber ribbon was dipped and rolled in a cross-linking solution that was left to stand for different periods of time. The cross-linking solution was a mixed solution of 0.92%wt TAHT and 3%wt sodium sulfate (the solvent in the mixed solution was water). The fiber ribbon was dipped and rolled 3 times, and the rolling rate was 130% (carried out in a cross-linking agent solution dipping and rolling tank). Then, a sodium hydroxide solution with a concentration of 0.8%wt was sprayed on the fiber ribbon. The catalyst solution in the cavity was sprayed out through a high-pressure pipe into a nozzle. The lyocell fiber ribbon entered the spray chamber and was divided into three fiber sub-ribbons at the bottom of the spray chamber through a number of rollers. Each fiber sub-ribbon had two sides. The fiber ribbons are transported from bottom to top in the spray chamber, and the catalyst solution sprayed from the nozzles penetrates the fiber ribbons horizontally and flows naturally downward along the fiber ribbons, and the catalyst solution is evenly sprayed on both sides of the fiber ribbons; the fiber ribbons are transported from bottom to top to the rollers at the top of the spray chamber for convergence and extrusion, and the extruded catalyst solution flows naturally downward along the fiber ribbons (fiber ribbons); the spraying speed is 0.313 kg of sodium hydroxide solution per 1 kg of fiber ribbon, and then enters the curing equipment to cure at 120 ° C for 45 minutes, enters the washing tank to wash 6 times at room temperature, and is dried to obtain cross-linked fibers.

[0139] Comparative Example 1

[0140] use Figure 1 The cross-linked fiber preparation device of the structure shown in the figure prepares the cross-linked fiber, comprising:

[0141] Padding tank 1, curing equipment 2 and washing tank 3;

[0142] At 80°C, the fiber ribbons were respectively dipped and rolled in a mixed solution of 0.92%wt TAHT, 0.3%wt Na2SO4 and 0.8%wt sodium hydroxide solution (the solvent of the mixed solution is water) that had been standing for different times for 10s, three dips and three rolls, with the rolling rate controlled at 125% (carried out in a dipping and rolling tank), and then entered the curing equipment for curing at 120°C for 30min, and then entered the washing tank for washing, and then dried to obtain cross-linked fibers.

[0143] The wet abrasion values ​​of the cross-linked fibers prepared in Example 3 and Comparative Example 1 were tested according to the above method. The test results are as follows:

[0144] Cross-linking method 0min 15min 60min Comparative Example 1 680.57 359.07 44.55 Example 3 535.66 532.58 528.67

[0145] It can be seen from the above results that the cross-linking effect of the padding spray method (Example 3) is very stable over time.

[0146] Example 4

[0147] The cross-linked fiber is prepared using the cross-linked fiber preparation device provided in Example 1:

[0148] The lyocell fiber ribbon is dipped into a 3%wt trisodium phosphate solution (the solvent in the solution is water), dipped 3 times and rolled 3 times, with a rolling rate of 125% (performed in a dipping and rolling tank), and then the fiber ribbon is sprayed with a 4.6%wt TAHT solution (the solvent in the solution is water), and the cross-linking agent solution in the cavity enters the nozzle through a high-pressure pipe and is sprayed out; the lyocell fiber ribbon enters the spray chamber and is divided into three fiber sub-ribbons at the bottom of the spray chamber through a number of rollers, each of which has two sides. The fiber sub-ribbons are transported from bottom to top in the spray chamber, and the nozzle The sprayed catalyst solution penetrates the fiber ribbon horizontally and flows naturally downward along the fiber ribbon, and the catalyst solution is evenly sprayed on both sides of the fiber ribbon; the fiber ribbon is transported from bottom to top to the roller at the top of the spray chamber for convergence and extrusion, and the squeezed catalyst solution flows naturally downward along the fiber ribbon (fiber ribbon); the spraying speed is 0.109kg to 1.182kg of cross-linking agent solution per 1kg net weight of fiber ribbon, and then enters the curing equipment to cure at 115℃ for 40min, and then enters the washing tank to wash 6 times at room temperature, and dry to obtain cross-linked fibers.

[0149] The wet abrasion value of the cross-linked fiber prepared in Example 4 was tested according to the above method, and the strength was carried out according to GB / T14337-2008 "Test Method for Tensile Properties of Chemical Staple Fibers". The test results are as follows:

[0150] TAHT solution mass kg / 1kg fiber 0.109 0.326 0.543 0.761 1.087 1.182 Wet wear value, r / dtex 317.89 456.13 498.36 512.31 522.43 537.14 Strength, cN / dtex 4.42 4.37 4.18 4.05 3.91 3.65

[0151] From the above results, it can be seen that the wet wear value gradually increases with the improvement of the cross-linking agent spraying quality, but when the TAHT solution mass kg / 1kg fiber = 1.182, the fiber strength decreases rapidly, resulting in the fiber strength failing to meet the requirements.

[0152] Example 5

[0153] The cross-linked fiber is prepared using the cross-linked fiber preparation device provided in Example 2:

[0154] At 80°C, the fiber ribbon is dipped into a cross-linking solution of 0.92%wt TAHT, 3%wt Na2SO4 (the solvent in the solution is water) that has been standing for 0min, 15min and 60min for 10s (performed in a cross-linking agent dipping and rolling tank), three dips and three rollings, and the rolling rate is controlled at 125%, and then enters a drying equipment for drying at 85°C for 15min, and then the fiber ribbon is dipped in a 3%wtNa3PO4 catalyst solution (the solvent in the solution is water) at room temperature (performed in a catalyst dipping and rolling tank), three dips and three rollings, and the rolling rate is controlled at 125%, and then enters a curing equipment for curing at 120°C for 30min, and then enters a water washing tank for washing, and then dried to obtain cross-linked fibers.

[0155] Comparative Example 2

[0156] use Figure 1 The cross-linked fiber preparation device of the structure shown in the figure prepares the cross-linked fiber:

[0157] At 80°C, the fiber ribbon was dipped and rolled in a cross-linking solution (the solvent in the solution is water) of 0.92%wt TAHT, 3%wt Na2SO4, and 3%wt Na3PO4 that had been standing for 0min, 15min, and 60min for 10s (carried out in a dipping and rolling tank), three dips and three rollings, with the rolling rate controlled at 125%. The fiber ribbon then entered a curing device and was cured at 120°C for 30min. The fiber ribbon was then washed in a water washing tank and dried to obtain cross-linked fibers.

[0158] The wet abrasion values ​​of the cross-linked fibers prepared in Example 5 and Comparative Example 2 were tested according to the above method. The test results are as follows:

[0159] Cross-linking method 0min 15min 60min Comparative Example 2 620.19 299.09 44.55 Example 5 393.57 386.74 395.17

[0160] It can be seen from the above results that the two-bath method (Example 5) effectively prevents the hydrolysis of the crosslinking agent.

[0161] Example 6

[0162] The cross-linked fiber is prepared using the cross-linked fiber preparation device provided in Example 1:

[0163] At 80°C, the lyocell fiber ribbon is dipped and rolled in a 4%wt trisodium phosphate solution (the solvent in the solution is water) (carried out in a dipping and rolling tank), 3 dips and 3 rollings, with a rolling rate of 120%, and then the fiber ribbon is sprayed with a 2%wt TAHT solution containing different concentrations of sodium sulfate (the solvent in the solution is water). The cross-linking agent solution in the cavity enters the nozzle through a high-pressure pipe and is sprayed out; the lyocell fiber ribbon enters the spray chamber and is divided into three fiber sub-ribbons at the bottom of the spray chamber through a number of rollers. Each fiber sub-ribbon has two sides. The fiber sub-ribbon is sprayed with a plurality of rollers. The catalyst solution sprayed from the nozzle is transported from bottom to top in the shower chamber, and the fiber sub-ribbon is horizontally penetrated by the catalyst solution and naturally flows downward along the fiber sub-ribbon. The cross-linking agent solution is evenly sprayed on both sides of the fiber sub-ribbon. The fiber sub-ribbon is transported from bottom to top to the roller at the top of the spray chamber for convergence and extrusion, and the extruded cross-linking agent solution naturally flows downward along the fiber ribbon (fiber sub-ribbon). The spraying speed is 0.28 kg of cross-linking agent solution for every 1 kg of net weight of fiber, and then enters the curing equipment to cure at 115 ° C for 40 minutes, and then enters the washing tank to wash 6 times at room temperature, and then dried to obtain cross-linked fibers.

[0164] The wet abrasion values ​​of cross-linked fibers prepared with different concentrations of sodium sulfate were tested according to the above method. The test results are as follows:

[0165] Sodium sulfate, wt Wet wear value, r / dtex 0 358.73 1％ 431.36 2％ 557.24 3％ 462.58 4％ 307.56

[0166] It can be seen that under certain conditions, the wet wear value of sodium sulfate at 2%wt is 557.24r / dtex, reaching the optimal value, which is 55.34% higher than that without adding sodium sulfate.

[0167] Example 7

[0168] The cross-linked fiber is prepared using the cross-linked fiber preparation device provided in Example 2:

[0169] At 80°C, the fiber ribbon is dipped in a cross-linking solution of 0.92%wt TAHT and 2%wt Na2SO4 (the solvent in the solution is water) for 10s (carried out in a cross-linking agent dipping and rolling tank), dipped and rolled three times, and the rolling rate is controlled at 135%, and then enters a drying device for drying at 85°C for 15min, and then the fiber ribbon is dipped in a certain concentration of Na3PO4 catalyst solution (the solvent in the solution is water) at room temperature (carried out in a catalyst dipping and rolling tank), dipped and rolled three times, and the rolling rate is controlled at 135%, and then enters a curing device for curing at 120°C for 30min, and then washed in a water washing tank, and then dried to obtain cross-linked fibers.

[0170] The wet abrasion values ​​of the cross-linked fibers prepared by trisodium phosphate solutions of different concentrations were tested according to the above method. The test results are as follows:

[0171]

[0172]

[0173] From the above results, it can be seen that under certain conditions, the wet wear value increases with the increase of trisodium phosphate dosage. When the trisodium phosphate reaches 4%wt, the wet wear value reaches the optimal value.

[0174] Compared with the prior art, the present invention avoids the hydrolysis and self-polymerization of the crosslinking agent under the action of the catalyst, thereby improving the crosslinking effect; it also reduces the influence of the catalytic bath on the crosslinking agent impregnated onto the fiber, thereby improving the stability of the crosslinked product and reducing the production cost.

[0175] The above is only a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the principle of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A two-stage method for preparing crosslinked fibers, comprising: The fiber ribbon is treated with a crosslinking agent solution and a catalyst solution respectively, wherein the method of treating the crosslinking agent solution is padding or spraying; The catalyst solution is treated by padding or spraying; drying is performed between padding in the crosslinking agent solution and padding in the catalyst solution; the padding temperature is 60-90°C; the crosslinking agent solution temperature is 60-90°C; during the spraying process, the spray liquid is sprayed on the fiber ribbon transported from bottom to top, and the spray liquid flows downward along the fiber ribbon; the fiber ribbon is divided into at least two fiber sub-ribbons; Then curing is performed to obtain cross-linked fibers; The crosslinking agent in the crosslinking agent solution is selected from 1,3,5-triacryloylhexahydro-1,3,5-triazine, the catalyst in the catalyst solution is selected from one or more of sodium hydroxide, trisodium phosphate and sodium carbonate, and the mass ratio of the fiber ribbon, the crosslinking agent in the crosslinking agent solution and the catalyst in the catalyst solution is 100: (0.1-7): (0.1-13); Alternatively, the crosslinker in the crosslinker solution is selected from methylated hexahydroxymethyl melamine resin, the catalyst in the catalyst solution is selected from one or more of methanesulfonic acid, p-toluenesulfonic acid and dodecylbenzene sulfone, and the mass ratio of the fiber ribbon, the crosslinker in the crosslinker solution and the catalyst in the catalyst solution is 100: (0.1-10): (0.6-8).

2. The method according to claim 1, characterized in that The two-stage method for preparing crosslinked fibers specifically comprises: The fiber ribbon is dipped in a crosslinking agent solution and then dried, and then dipped in a catalyst solution and then cured to obtain a crosslinked fiber; or The fiber ribbon is dipped in a catalyst solution and then dried, and then dipped in a crosslinking agent solution and then cured to obtain a crosslinked fiber.

3. The method according to claim 1, characterized in that: The two-stage method for preparing crosslinked fibers specifically comprises: The fiber ribbon is dipped in a crosslinking agent solution and then sprayed with a catalyst solution, and then cured to obtain a crosslinked fiber; or The fiber ribbon is dipped in a catalyst solution and then sprayed with a crosslinking agent solution, and then cured to obtain a crosslinked fiber.

4. The method according to claim 1, characterized in that: Also includes: adding sodium sulfate to the cross-linking agent solution; The mass ratio of the fiber ribbon to sodium sulfate is 100:(1-13).

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