CN107956127B - Preparation method of polyurethane elastic fiber with skin-core structure - Google Patents
Preparation method of polyurethane elastic fiber with skin-core structure Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention discloses a preparation method of polyurethane elastic fiber with a skin-core structure. By adjusting the types and the contents of the sheath and core layer spinning solution additives, the additives are enriched in the sheath layer, and the purposes of enhancing the environmental tolerance of the fiber, changing the surface property of the fiber and reducing the use cost of the additives are achieved. The key point of the preparation of the polyurethane elastic fiber with the skin-core structure is as follows: 1) preparing an N, N-dimethylacetamide solution of polyurethane-polyurea, curing to obtain a core layer spinning solution, carrying out spinning and stretching by a spinneret plate, and drying at high temperature in a first channel to prepare a core layer polyurethane elastic fiber; 2) taking part of the polyurethane-polyurea solution, adding an auxiliary agent for enhancing the environmental tolerance of the fiber or changing the surface property of the fiber to prepare a skin layer spinning solution, coating the skin layer spinning solution on the surface of the core layer fiber through a special structure coating device, drying the core layer fiber at high temperature through a second channel, oiling and winding the core layer fiber to obtain the skin-core structure polyurethane elastic fiber.
Description
Technical Field
The invention belongs to a preparation method of polyurethane elastic fiber, and particularly relates to a preparation method of polyurethane elastic fiber with a skin-core structure.
Background
Polyurethane elastic fiber, spandex for short, is a class of elastic synthetic fiber, has excellent properties of high elongation at break, high elastic recovery, corrosion resistance, aging resistance, heat resistance, fatigue resistance and the like, and is widely applied to the textile industry. With the increasing demand of consumers for the comfort of fabrics, the conventional polyurethane elastic fiber can not meet the market demand, and the development of differential polyurethane elastic fiber is in the trend. The development of differentiated polyurethane elastic fibers can be promoted by the sheath-core structure. The skin-core structure polyurethane elastic fiber consists of two components, namely a skin layer and a core layer, the cross section is generally a concentric circle with the inner circle formed by the core layer and the outer circle formed by the skin layer, and the polyurethane elastic fiber also has eccentric circle, special shape and uniform cross section shape. The difference between the skin layer and the core layer mainly lies in the material composition and the component proportion. In terms of material composition, the core layer material is generally conventional polyurethane-urea, and the skin layer material comprises thermoplastic polyurethane, polyester, aramid fiber, polypropylene and the like, and the combination can enable the polyurethane elastic fiber to have the properties of both the skin layer material and the core layer material. Granted patent US1345944 discloses a preparation method of a foamed polypropylene-polyurethane elastic fiber skin-core composite fiber, which comprises coating a polypropylene solution on the surface of a polyurethane elastic fiber and reducing the pressure to foam the polypropylene, so that the surface of the polyurethane elastic fiber can be coated with microcellular foamed polypropylene, and the resilience force and the degradation resistance of the polyurethane elastic fiber are effectively improved. The granted patent WO2010/045637 discloses a preparation method of a thermoplastic polyurethane-polyurethane elastic fiber skin-core composite fiber, wherein low-melting-point thermoplastic polyurethane and polyurethane-polyurea solution are extruded by a skin-core spinneret assembly for dry spinning, the obtained composite fiber skin layer is low-melting-point thermoplastic polyurethane, and the low-melting-point thermoplastic polyurethane is hot-melt and can be fused with other blended fibers after heat treatment, so that the problem of spinning caused by the breakage of the polyurethane elastic fiber is solved. Patent CN201611046719 discloses a preparation method of an aramid fiber-polyurethane elastic fiber skin-core composite fiber, wherein an aramid fiber solution and a polyurethane-polyurea solution are extruded by a skin-core spinneret assembly to carry out dry spinning, an obtained composite fiber skin layer is aramid fiber, and the high temperature resistance, chemical corrosion resistance and wear resistance of the polyurethane elastic fiber are effectively improved. In terms of the component proportion, the main components of the skin layer and the core layer are unchanged and are polyurethane-urea, and the difference is the type and the content of the auxiliary agent. Partial auxiliary agents can better play a role in the enrichment of the skin layer, such as an antioxidant auxiliary agent, an ultraviolet-resistant auxiliary agent and a chlorine-resistant auxiliary agent for enhancing the environmental tolerance of the polyurethane elastic fiber, and such as a hydrophilic auxiliary agent, an unwinding auxiliary agent and a delustering auxiliary agent for changing the surface property of the polyurethane elastic fiber. By adopting the skin-core structure, the auxiliary agent can be enriched in the skin layer at a higher concentration, and the core layer does not contain or only contains a small amount of the auxiliary agent, so that the use efficiency of the auxiliary agent is improved, the use cost of the auxiliary agent is reduced, and the influence of the auxiliary agent on the mechanical property of the polyurethane elastic fiber is reduced. Granted patent WO2011/149734 discloses a method for improving unwinding performance of polyurethane elastic fiber without affecting mechanical properties of the polyurethane elastic fiber, the fiber adopts a skin-core structure, and inorganic particles with higher content as an unwinding aid are added to a skin layer to achieve the purpose of unwinding, and since the core layer does not contain inorganic particles, the cost is reduced, and the mechanical properties of the polyurethane elastic fiber are ensured.
Generally, the production process of the polyurethane elastic fiber with the sheath-core structure comprises the steps of preparing two spinning solutions of the sheath and the core, and extruding the spinning solutions through a sheath-core spinneret by a metering pump at a certain flow rate for dry spinning. A typical construction of a sheath-core spinneret is described in the granted patent US 5256050. The core layer spinning solution enters the spinning nozzle from a top pore passage, the skin layer spinning solution enters the spinning nozzle from a side pore passage, the two spinning solutions are mixed at the spinning nozzle to form a columnar fluid with the core layer spinning solution inside and the skin layer spinning solution outside, and the columnar fluid flows out of the spinning nozzle and enters the channel. The obtained polyurethane elastic fiber with a skin-core structure and a complete structure has higher requirements on spinning solution: 1) the rheological properties are similar, i.e. the apparent viscosities of the two spinning solutions do not differ much at a certain flow rate. Otherwise, the two spinning solutions are easily mixed in the radial direction, so that the low-viscosity spinning solution is separated into discontinuous areas by the high-viscosity spinning solution, and the integrity of the skin-core structure is influenced; 2) if two solvents are used, when the volatilization rate of the skin layer solvent is higher than that of the core layer, the problem that the core layer solvent cannot be volatilized due to skin layer solidification is caused, and on the other hand, the existing dry spinning system is difficult to recycle the two-component solvent; 3) the spinnability is the same, and because two spinning solutions pass through the same high-temperature channel, if any spinning solution has insufficient spinnability, the problems of yarn hanging, yarn doubling, yarn breaking and the like are caused, and the structural integrity of the sheath core is damaged. As for the spinning assembly, the distribution plate and the sheath-core spinneret have high precision requirements, the equipment cost is far higher than that of the common assembly, and the distribution plate and the sheath-core spinneret are easy to damage in the processes of assembly, disassembly, washing and maintenance. Therefore, the polyurethane elastic fiber with the skin-core structure produced by the skin-core spinneret plate has extremely high requirements on the performance of the spinning solution and the precision of equipment, and the stability of the product is difficult to ensure.
In addition to the common sheath-core spinneret, the granted patent US3507741 uses a coating method to produce the polyurethane elastic fiber with a sheath-core structure, and the core component is the coating spinneret. The core layer is made of polyurethane elastic fiber and enters a spinning nozzle through a top pore passage, the skin layer spinning solution enters the spinning nozzle through a side pore passage, the polyurethane elastic fiber is coated by the spinning solution at the spinning nozzle to form a columnar fluid, the inner part of the columnar fluid is made of the polyurethane elastic fiber, the outer ring of the columnar fluid is made of the skin layer spinning solution, and the columnar fluid flows out of the spinning nozzle and enters the channel. Compared with a skin-core spinneret plate, the coating spinneret plate has the greatest advantage that polyurethane elastic fibers are used for replacing a core layer spinning solution, and the requirement that the skin-core spinning solution has consistency in rheological property, solvent and spinnability is avoided. However, consideration should be given to how the polyurethane elastic fiber passes through the coating spinneret. If the fiber is coiled, putting the monofilament into the top hole channel, sucking the monofilament out of the coating spinneret plate through a suction gun; however, in order to unwind the coiled polyurethane elastic fiber conveniently, the surface of the monofilament is coated with an oiling agent, and the bonding force between the skin layer and the core layer is not strong due to the existence of the oiling agent. If the monofilaments just after passing through the channel directly pass through the coating spinneret plate, the monofilaments are not oiled by an oil roller, so that the oiling agent problem can be avoided, but the channel has extremely high filament discharging speed of 700-900 m/min, and the monofilament ports need to be found in an extremely short time and pass through the spinneret plate, otherwise, a large amount of monofilaments are accumulated; considering that the number of the monofilaments passing through the channel is at least 24-36, the method for passing all the monofilaments through the corresponding spinneret plate in a short time has no operational feasibility.
Also in the production of polyurethane elastic fibers with a sheath-core structure by coating, patent CN201710128364 uses a coating roller for coating, which avoids the operation of passing the monofilament through the spinneret. The monofilament from the spinning channel enters a coating system through traction, the coating system mainly comprises a liquid carrying tank and two coating rollers, the coating rollers rotate, the skin layer spinning solution is uniformly loaded on the surfaces of the coating rollers to form liquid films, and the surfaces of the fibers are uniformly coated by utilizing the contact action between the fibers and the coating rollers. And then the fiber is dried and cured by a thermocuring device. And oiling, drafting and winding the cured fiber to obtain the polyurethane elastic fiber with the sheath-core structure. However, the coating of the fibers with the coating roller has the following disadvantages: 1) the viscosity of the spinning solution on the surface layer cannot be too high, otherwise, a liquid film with uniform thickness is difficult to form on the surface of the coating roller, and the surface of the fiber cannot be uniformly coated; 2) the surface part of the fiber is contacted with the surface of the coating roller, and the part of the fiber is contacted with the liquid film, so that the spinning solution is unevenly distributed in the radial direction of the fiber, and the radial distribution uniformity of the product is influenced; 3) the heat curing device has limited solvent volatilization capacity, the heat curing device comprises a hot air drying system, the use temperature is 80-100 ℃, a hot roller drying system is used, the surface temperature of the hot roller is 60-80 ℃, and the heat supply capacity is insufficient under the condition that fibers pass through at a high speed or the cortex solvent is difficult to volatilize.
In summary, the production cost of the polyurethane elastic fiber can be reduced through the sheath-core structure, and the special performance is given to the polyurethane elastic fiber, which is beneficial to the differential development of the polyurethane elastic fiber. The polyurethane elastic fiber with the skin-core structure is mainly produced by a skin-core spinneret plate, a coating spinneret plate and a coating roller. However, the sheath-core spinneret plate has high requirements on raw materials and equipment, and the stability of the product is difficult to ensure; the coating spinneret plate has the problem of how to pass the polyurethane elastic fiber through the spinneret plate, so that the operation difficulty is very high; the coating roller requires the viscosity of the spinning solution to be within a suitable range, and product uniformity cannot be guaranteed.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a preparation method of polyurethane elastic fiber with a skin-core structure. Solves the problems of high requirements on raw materials and equipment, poor product uniformity and the like when preparing the polyurethane elastic fiber with the skin-core structure. The method for preparing the polyurethane elastic fiber with the skin-core structure has the characteristics of high production efficiency, uniform product, adjustable fiber section shape and the like, and is a method for industrial production.
The technical scheme is as follows: the invention relates to a preparation method of polyurethane elastic fiber with a skin-core structure, which comprises the following steps of 1), preparing N, N-dimethylacetamide solution of polyurethane-polyurea by using diisocyanate, polyether diol, diamine and monoamine as raw materials through prepolymerization and chain extension in the preparation process, curing to obtain core layer spinning solution, carrying out spinning and stretching on the core layer spinning solution by means of a spinneret plate, and drying at high temperature in a first channel to prepare core layer polyurethane elastic fiber; 2) taking part of polyurethane-polyurea solution, adding conventional additives such as an antioxidant, an ultraviolet absorbent, a lubricant, a flatting agent and the like, adding special additives such as a chlorine-resistant additive, a hydrophilic additive, a dyeing additive, a thermal bonding additive and the like according to product requirements to prepare a skin layer spinning solution, coating the skin layer spinning solution on the surface of the polyurethane elastic fiber yarn through a special structure coating roller, drying at high temperature through a second channel to prepare the polyurethane elastic fiber yarn with the skin-core structure, and finally, oiling, winding and forming to obtain the polyurethane elastic fiber yarn coil with the skin-core structure.
The method specifically comprises the following steps:
1) simultaneously adding diisocyanate and polyether polyol into a first reactor, and fully performing prepolymerization reaction at the temperature of 70-80 ℃ to obtain a prepolymer capped with-NCO, wherein the-NCO content of the prepolymer capped with-NCO is 1.8-3.5 wt%;
2) fully dissolving the-NCO-terminated prepolymer in a high-speed dissolving machine by using N, N-dimethylacetamide as a solvent to obtain a-NCO-terminated prepolymer N, N-dimethylacetamide solution, wherein the content of the prepolymer is 35-45 wt%;
3) in a second reactor, adopting a mixed amine N, N-dimethylacetamide solution, wherein the mixed amine comprises diamine as a chain extender and monoamine as a chain terminator, carrying out chain extension on the-NCO end-capped prepolymer N, N-dimethylacetamide solution to obtain a polyurethane-polyurea solution, and curing to obtain a core layer spinning solution;
4) feeding the core layer spinning solution into a dry spinning system through a metering pump, carrying out spinning and stretching on the core layer spinning solution by means of a spinneret plate, and drying at high temperature in a first channel to prepare core layer polyurethane elastic fiber;
5) adding an auxiliary agent for enhancing the environmental tolerance of the fiber and an auxiliary agent for selectively changing the surface property of the fiber into the polyurethane-polyurea solution, and fully stirring, dispersing and curing to obtain a skin layer spinning solution; the auxiliary agent for enhancing the environmental tolerance of the fiber comprises an antioxidant, an ultraviolet absorbent and a chlorine-resistant auxiliary agent, and the auxiliary agent for changing the surface property of the fiber comprises a lubricant, a delustering agent and a hydrophilic auxiliary agent;
6) coating the surface of the polyurethane elastic fiber of the core layer with the skin layer spinning solution by a coating device;
7) and drying the polyurethane elastic fiber at high temperature through a second channel to prepare the polyurethane elastic fiber with the skin-core structure, and finally, oiling, winding and forming to obtain the skin-core structure wire coil.
Wherein the content of the first and second substances,
the diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, 4,4 '-cyclohexanedimethylene diisocyanate and 2, 4' -cyclohexanedimethylene diisocyanate.
The polyether polyol is polytetramethylene ether glycol, and the molecular weight of the polyether polyol is 1500-3000.
the-NCO end capping prepolymer has an-NCO content of 1.8 to 3.5 weight percent; the content of the prepolymer in the-NCO end-capped prepolymer N, N-dimethylacetamide solution is 35-45 wt%;
the diamine used as the chain extender is one or more of ethylenediamine, 1, 2-propanediamine and 2-methyl-1, 5-pentanediamine; the monoamine in the chain terminator is one or more of dimethylamine, diethylamine, dipropylamine, ethanolamine or diethanolamine; the molar ratio of the diamine to the monoamine is 10: 1-20: 1.
The content of the mixed amine in the mixed amine N, N-dimethylacetamide solution is 4-6 wt%.
The viscosity of the cured skin layer and core layer spinning solution is 1500-6000 poise.
The preparation method of the polyurethane elastic fiber with the skin-core structure comprises the following preparation processes: after the core layer polyurethane elastic fiber is discharged from the first channel, the core layer polyurethane elastic fiber is wound on the third roller through traction, the third roller is lifted to the top of the second channel through the guide rail, the core layer polyurethane elastic fiber is subjected to skin coating through the fourth roller leading-in coating device under the traction of the suction gun, and then directly enters the second channel, the polyurethane elastic fiber is discharged from the second channel, the advancing direction of the polyurethane elastic fiber is changed through the fifth roller, the polyurethane elastic fiber is oiled through the oiling roller, the advancing direction of the polyurethane elastic fiber is changed through the sixth roller, and finally the polyurethane elastic fiber is wound and formed through winding equipment.
Wherein the content of the first and second substances,
the coating device is composed of a left half cylinder and a right half cylinder, wherein the left half cylinder and the right half cylinder are internally provided with cavities, the two half cylinders can be in an opening or closing state, when in the opening state, the core layer polyurethane elastic fiber is moved into the cavities through a gap, at the moment, the core layer polyurethane elastic fiber penetrates through the tops of the two half cylinders, penetrates through the cavities and penetrates out of the bottoms of the two half cylinders, and then the two half cylinders are closed; the skin layer spinning solution enters the cavity of the coating device through the corresponding inlet, and the compressed air enters the cavity of the coating device through the corresponding inlet, so that the aim of enabling the polyurethane elastic fiber to penetrate through the coating device is fulfilled; the contact section of the two semi-cylinders contains sealant so as to ensure that the skin layer spinning solution does not flow out of the contact section when the two semi-cylinders are closed; the diameter of the polyurethane elastic fiber outlet is determined according to the thickness of the required skin layer and is 0.05-0.5 mm; the cross section of the outlet of the coating device is circular or irregular.
The compressed air is connected into the cavity of the coating device through the corresponding inlet, the outflow flow of the skin layer spinning solution is adjusted through the pressure of the cavity, the pressure of the cavity is adjusted through the compressed air, and the adjusting range is 0.15-0.30 mPa.
The second channel is a conventional dry spinning channel and is positioned right below the coating device, the temperature of the upper channel of the second channel is 250-270 ℃, and the temperature of the lower channel is 180-200 ℃.
No component in contact with polyurethane elastic fiber is arranged between the coating device and the second channel, so that the skin-core structure is not damaged before entering the second channel; the inlet of the coating device and the outlet of the second channel contain the first yarn guide and the second yarn guide, and the horizontal disturbance of the polyurethane elastic fiber in the coating device is inhibited through the stabilization of the yarn guides.
Has the advantages that:
1) the technology can improve the production efficiency of the polyurethane elastic fiber with the skin-core structure.
Compared with the coating spinneret plate disclosed in the patent US3507741, the coating device disclosed in the patent can ensure that the fibers can pass through in a short time through the openable structural design, and the time consumed by fiber traction and winding up is shortened.
Compared with the thermocuring equipment disclosed in patent CN201710128364, the temperature of the second shaft is higher, the temperature of the upper shaft reaches 250-270 ℃, the temperature of the lower shaft reaches 180-200 ℃, and when fibers pass through the shafts at high speed, heat supply required by volatilization of a skin layer spinning solution solvent is guaranteed, and the yarn production efficiency is improved; in addition, the skin spinning solution solvent can be recovered through a channel air return system, so that the production cost is reduced.
2) The technology can improve the uniformity of the polyurethane elastic fiber with the sheath-core structure.
Compare in patent US5256050 and use skin-core spinneret to prepare skin-core structure polyurethane elastic fiber, this patent adopts the method of top layer coating to the fibre replaces sandwich layer spinning solution, has solved the high problem of skin-core spinneret to raw materials, equipment requirement, has guaranteed the continuity of skin-core structure.
Compared with the patent CN201710128364 in which a coating roller is used for preparing the polyurethane elastic fiber with the skin-core structure, the coating device has no contact with the outlet of the coating device in the coating process, and a component which can be in contact with the polyurethane elastic fiber is not arranged between the outlet of the coating device and the outlet of the shaft, so that the radial distribution uniformity of the product is ensured.
This technique uses the inside cavity diameter of coating device to be greater than polyurethane elastic fiber and goes out, the entry diameter, can be used to store cortex spinning liquid, prevents that cortex spinning liquid from flowing out coating equipment through polyurethane elastic fiber entry, can reduce the instability that cortex spinning liquid outflow brought because of the disturbance of inflow simultaneously, guarantees the homogeneous of coating volume.
3) The technology can be used for producing the polyurethane elastic fiber with the skin-core structure and the adjustable cross section shape and thickness.
The technology can prepare the polyurethane elastic fiber with the special-shaped section and the skin-core structure with the controllable skin layer thickness. By changing the shape of the outlet section of the coating device, such as a star-shaped section, the polyurethane elastic fiber with a special-shaped structure can be prepared; the skin-core structure polyurethane elastic fiber with different skin layer thicknesses can be prepared by changing the area of the cross section of the outlet of the coating device and matching the flow of the outlet of the skin layer spinning solution.
The technology can prepare the polyurethane elastic fiber with a multilayer sheath-core structure, and is realized by adding a new coating device and a channel unit at the outlet of a second channel.
Drawings
FIG. 1 is a schematic structural view of the special coating device of the present invention in an open state,
FIG. 2 is a schematic structural view of the special coating device of the present invention in a closed state.
FIG. 3 is a schematic view of a process for preparing a polyurethane elastic fiber with a sheath-core structure according to the present invention.
Detailed Description
Example 1 Low-cost sheath-core polyurethane elastic fiber
Step 1, simultaneously feeding 237.10kg of polytetramethylene ether glycol (molecular weight is 1800) and 53.90kg of 4, 4-diphenylmethane diisocyanate into a first reactor, and reacting for 2.2h at the temperature of 70 ℃ to obtain a prepolymer (PP);
step 2, simultaneously conveying 291.00kg of prepolymer and 341.50kg of N, N-Dimethylacetamide (DMAC) solvent to a high-speed dissolving machine, and fully dissolving PP by high-speed shearing to obtain Prepolymer Solution (PPs);
step 3, rapidly stirring 632.50kg of prepolymer solution and 16.60kg of mixed amine DMAC solution (comprising 0.61kg of propane diamine, 4.59kg of ethylene diamine and 0.60kg of ethylene diamine) to simultaneously generate chain growth and chain termination, preparing polyurethane-polyurea solution, and curing to obtain core layer spinning solution;
step 4, adding 5.90kg of antioxidant, ultraviolet absorbent, lubricant and flatting agent into 10.96kg of DMAC, and fully grinding by using a ball mill to prepare slurry with the solid content of 35 wt%;
step 5, repeating the step 3 to prepare 632.21kg of polyurethane-polyurea solution, adding 16.86kg of slurry, and fully stirring, dispersing and curing to obtain a skin layer spinning solution;
step 6, extruding the core layer spinning solution from a gear pump, carrying out dry spinning through a first channel, wherein a spinneret plate is provided with 3 holes and 36 ends, the upper channel temperature is 260 ℃, the lower channel temperature is 190 ℃, the spinning speed is 800m/min, and the polyurethane elastic fiber out of the first channel is drawn according to the mode shown in the figure 3, wherein the speed ratio of a fifth roller to a fourth roller is 1.10;
step 7, after the spinning process is stable, adding the skin layer spinning solution into the cavity of the coating device, adjusting the discharge amount of the skin layer spinning solution to be 1.1 times of the discharge amount of the core layer spinning solution, and maintaining the air pressure of the cavity of the coating device at 0.30 mPa;
and 8, performing dry spinning on the polyurethane elastic fiber out of the coating device through a second shaft at the upper shaft temperature of 250 ℃ and the lower shaft temperature of 180 ℃, oiling the polyurethane elastic fiber with a skin-core structure, and winding and forming.
Example 2 chlorine-resistant sheath-core structured polyurethane elastic fiber
Step 1, simultaneously feeding 237.10kg of polytetramethylene ether glycol (molecular weight is 1800) and 54.20kg of 4, 4-diphenylmethane diisocyanate into a first reactor, reacting for 2.2h at 75 ℃ to obtain a prepolymer (PP);
step 2, simultaneously conveying 291.30kg of prepolymer and 347.80kg of N, N-Dimethylacetamide (DMAC) solvent to a high-speed dissolving machine, and fully dissolving PP by high-speed shearing to obtain Prepolymer Solution (PPs);
step 3, rapidly stirring 639.10kg of prepolymer solution and 17.20kg of mixed amine DMAC solution (comprising 0.61kg of propane diamine, 5.19kg of ethylene diamine and 0.60kg of ethylene diamine) to simultaneously generate chain growth and chain termination, preparing polyurethane-polyurea solution, and curing to obtain core layer spinning solution;
step 4, adding 5.90kg of antioxidant, ultraviolet absorbent, lubricant, flatting agent and 0.5kg of hydrotalcite into 11.88kg of DMAC, and fully grinding by a ball mill to prepare slurry with the solid content of 35 wt%;
step 5, repeating the step 3 to prepare 656.30kg of polyurethane-polyurea solution, adding 18.28kg of slurry, and fully stirring, dispersing and curing to obtain a skin layer spinning solution;
step 6, extruding the core layer spinning solution from a gear pump, carrying out dry spinning through a first channel, wherein a spinneret plate is provided with 3 holes and 36 ends, the upper channel temperature is 260 ℃, the lower channel temperature is 190 ℃, the spinning speed is 500m/min, and the polyurethane elastic fiber out of the first channel is drawn according to the mode shown in the figure 3, wherein the speed ratio of a fifth roller to a fourth roller is 1.10;
step 7, after the spinning process is stable, adding the skin layer spinning solution into the cavity of the coating device, adjusting the discharge amount of the skin layer spinning solution to be 1.1 times of the discharge amount of the core layer spinning solution, and maintaining the air pressure of the cavity of the coating device at 0.30 mPa;
and 8, performing dry spinning on the polyurethane elastic fiber out of the coating device through a second shaft at the upper shaft temperature of 250 ℃ and the lower shaft temperature of 180 ℃, oiling the polyurethane elastic fiber with a skin-core structure, and winding and forming.
Example 3 hydrophilic sheath-core polyurethane elastic fiber
Step 1, simultaneously feeding 237.10kg of polytetramethylene ether glycol (molecular weight is 1800) and 54.20kg of 4, 4-diphenylmethane diisocyanate into a first reactor, reacting for 2.2h at 75 ℃ to obtain a prepolymer (PP);
step 2, simultaneously conveying 291.30kg of prepolymer and 347.80kg of N, N-Dimethylacetamide (DMAC) solvent to a high-speed dissolving machine, and fully dissolving PP by high-speed shearing to obtain Prepolymer Solution (PPs);
step 3, rapidly stirring 639.10kg of prepolymer solution and 17.20kg of mixed amine DMAC solution (comprising 0.61kg of propane diamine, 5.19kg of ethylene diamine and 0.60kg of ethylene diamine) to simultaneously generate chain growth and chain termination, preparing polyurethane-polyurea solution, and curing to obtain core layer spinning solution;
step 4, adding 5.90kg of antioxidant, ultraviolet absorbent, lubricant, flatting agent and 0.5kg of polyacrylic acid into 11.88kg of DMAC, and fully grinding by using a ball mill to prepare slurry with the solid content of 35 wt%;
step 5, repeating the step 3 to prepare 656.30kg of polyurethane-polyurea solution, adding 18.28kg of slurry, and fully stirring, dispersing and curing to obtain a skin layer spinning solution;
step 6, extruding the core layer spinning solution from a gear pump, carrying out dry spinning through a first channel, wherein a spinneret plate is provided with 3 holes and 36 ends, the upper channel temperature is 260 ℃, the lower channel temperature is 190 ℃, the spinning speed is 800m/min, and the polyurethane elastic fiber out of the first channel is drawn according to the mode shown in the figure 3, wherein the speed ratio of a fifth roller to a fourth roller is 1.10;
step 7, after the spinning process is stable, adding the skin layer spinning solution into the cavity of the coating device, adjusting the discharge amount of the skin layer spinning solution to be 1.1 times of the discharge amount of the core layer spinning solution, and maintaining the air pressure of the cavity of the coating device at 0.30 mPa;
and 8, performing dry spinning on the polyurethane elastic fiber out of the coating device through a second shaft at the upper shaft temperature of 250 ℃ and the lower shaft temperature of 180 ℃, oiling the polyurethane elastic fiber with a skin-core structure, and winding and forming.
Claims (9)
1. A preparation method of polyurethane elastic fiber with a skin-core structure is characterized by comprising the following steps:
1) simultaneously adding diisocyanate and polyether polyol into a first reactor, and fully performing prepolymerization reaction at the temperature of 70-80 ℃ to obtain a prepolymer terminated by-NCO; the-NCO end capping prepolymer has an-NCO content of 1.8 to 3.5 weight percent;
2) fully dissolving the-NCO-terminated prepolymer in a high-speed dissolving machine by using N, N-dimethylacetamide as a solvent to obtain a-NCO-terminated prepolymer N, N-dimethylacetamide solution; the prepolymer content is 35 wt% -45 wt%;
3) in a second reactor, adopting a mixed amine N, N-dimethylacetamide solution, wherein the mixed amine comprises diamine as a chain extender and monoamine as a chain terminator, carrying out chain extension on the-NCO end-capped prepolymer N, N-dimethylacetamide solution to obtain a polyurethane-polyurea solution, and curing to obtain a core layer spinning solution;
4) feeding the core layer spinning solution into a dry spinning system through a metering pump, carrying out spinning and stretching on the core layer spinning solution by means of a spinneret plate, and drying at high temperature in a first channel to prepare core layer polyurethane elastic fiber;
5) adding an auxiliary agent for enhancing the environmental tolerance of the fiber and an auxiliary agent for selectively changing the surface property of the fiber into the polyurethane-polyurea solution, and fully stirring, dispersing and curing to obtain a skin layer spinning solution; the auxiliary agent for enhancing the environmental tolerance of the fiber comprises an antioxidant, an ultraviolet absorbent and a chlorine-resistant auxiliary agent, and the auxiliary agent for changing the surface property of the fiber comprises a lubricant, a delustering agent and a hydrophilic auxiliary agent;
6) coating the surface of the polyurethane elastic fiber of the core layer with the skin layer spinning solution by a coating device;
7) drying the polyurethane elastic fiber at high temperature through a second channel to prepare the polyurethane elastic fiber with the skin-core structure, and finally, oiling and winding to obtain a skin-core structure wire coil;
the coating device is composed of a left half cylinder and a right half cylinder, wherein the left half cylinder and the right half cylinder are internally provided with cavities, the two half cylinders can be in an opening or closing state, when in the opening state, the core layer polyurethane elastic fiber is moved into the cavities through a gap, at the moment, the core layer polyurethane elastic fiber penetrates through the tops of the two half cylinders, penetrates through the cavities and penetrates out of the bottoms of the two half cylinders, and then the two half cylinders are closed; the skin layer spinning solution enters the cavity of the coating device through the corresponding inlet, and the compressed air enters the cavity of the coating device through the corresponding inlet, so that the aim of enabling the polyurethane elastic fiber to penetrate through the coating device is fulfilled; the contact section of the two semi-cylinders contains sealant so as to ensure that the skin layer spinning solution does not flow out of the contact section when the two semi-cylinders are closed; the diameter of the polyurethane elastic fiber outlet is determined according to the thickness of the required skin layer and is 0.05-0.5 mm; the cross section of the outlet of the coating device is circular or irregular.
2. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 1, wherein: the diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, 4,4 '-cyclohexanedimethylene diisocyanate and 2, 4' -cyclohexanedimethylene diisocyanate.
3. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 1, wherein: the polyether polyol is polytetramethylene ether glycol, and the molecular weight of the polyether polyol is 1500-3000.
4. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 1, wherein: the diamine used as the chain extender is one or more of ethylenediamine, 1, 2-propanediamine and 2-methyl-1, 5-pentanediamine; the monoamine in the chain terminator is one or more of dimethylamine, diethylamine, dipropylamine, ethanolamine or diethanolamine; the molar ratio of the diamine to the monoamine is 10: 1-20: 1.
5. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 1, wherein: the content of the mixed amine in the mixed amine N, N-dimethylacetamide solution is 4-6 wt%.
6. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 1, wherein: the preparation method of the polyurethane elastic fiber with the skin-core structure comprises the following preparation processes: after the core layer polyurethane elastic fiber is discharged from the first channel, the core layer polyurethane elastic fiber is wound on the third roller through traction, the third roller is lifted to the top of the second channel through the guide rail, the core layer polyurethane elastic fiber is subjected to skin coating through the fourth roller leading-in coating device under the traction of the suction gun, and then directly enters the second channel, the polyurethane elastic fiber is discharged from the second channel, the advancing direction of the polyurethane elastic fiber is changed through the fifth roller, the polyurethane elastic fiber is oiled through the oiling roller, the advancing direction of the polyurethane elastic fiber is changed through the sixth roller, and finally the polyurethane elastic fiber is wound and formed through winding equipment.
7. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 1, wherein: compressed air is connected into the cavity of the coating device through the corresponding inlet, the outflow flow of the skin layer spinning solution is adjusted through the pressure of the cavity, the pressure of the cavity is adjusted through the compressed air, and the adjusting range is 0.15-0.30 MPa.
8. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 6, wherein: the second channel is a conventional dry spinning channel and is positioned right below the coating device, the temperature of the upper channel of the second channel is 250-270 ℃, and the temperature of the lower channel is 180-200 ℃.
9. The method for preparing polyurethane elastic fiber with sheath-core structure as claimed in claim 6, wherein: no component in contact with polyurethane elastic fiber is arranged between the coating device and the second channel, so that the skin-core structure is not damaged before entering the second channel; the inlet of the coating device and the outlet of the second channel contain the first yarn guide and the second yarn guide, and the horizontal disturbance of the polyurethane elastic fiber in the coating device is inhibited through the stabilization of the yarn guides.
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| CN108977929B (en) * | 2018-05-30 | 2020-12-15 | 浙江华峰氨纶股份有限公司 | Preparation method of moisture-absorbing and sweat-releasing polyurethane elastic fiber with skin-core structure |
| CN109797457A (en) * | 2019-01-17 | 2019-05-24 | 连云港杜钟新奥神氨纶有限公司 | A kind of moisture absorbing and sweat releasing polyurethane elastomeric fiber of bi-component |
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| CN115353609B (en) * | 2022-07-22 | 2023-06-09 | 华东师范大学 | Repairable and reinforced high-performance polyurethane elastomer and preparation method thereof |
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