A bicomponent microspun spunbonded hydroentangled nonwoven material and method of making same
By modifying montmorillonite and copolymers, a two-component ultrafine spunbond hydroentangled nonwoven material was developed, which solved the problems of poor hydrophilicity and moisture permeability and the difficulty in balancing fiber diameter and mechanical properties. This achieved a balance between fiber splitting ability and mechanical properties, and improved the hydrophilicity and mechanical properties of the material.
Patent Information
- Application Number
- CN202511403294.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-29
- Publication Date
- 2025-12-09
- Estimated Expiration
- 2045-09-29
AI Technical Summary
Existing bicomponent spunbond hydroentangled nonwoven materials suffer from poor hydrophilicity and moisture permeability, and the fiber diameter and mechanical properties are difficult to balance, especially during the spinning process, they are prone to breakage.
Modified montmorillonite was used as a reinforcing filler to prepare modified polyester and modified nylon masterbatches through spunbonding and hydroentangling methods, forming bicomponent ultrafine fibers. The fibers were further modified with styrene-maleic anhydride copolymer and dibromoneopentyl glycol to improve their hydrophilicity and mechanical properties.
It achieves a balance between fiber splitting ability and mechanical properties, improves the hydrophilicity and mechanical properties of nonwoven materials, and reduces the risk of fiber breakage during spinning.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of non-woven materials, and particularly relates to a bicomponent ultrafine spun-bonded hydroentangled non-woven material and a preparation method thereof. BACKGROUND
[0002] Non-woven material refers to sheet or roll material obtained by directly forming a fiber web and then reinforcing the web through heating without going through traditional spinning-weaving processes. According to the web forming process, the non-woven material can be divided into several categories, such as spun-bonded (spun-bonded), melt-blown, hydroentangled, needle-punched and thermal-bonded. The spun-bonded process is to stretch the molten polymer into ultrafine fibers by high-speed hot air, and then cool the web directly. The spun-bonded process has the characteristics of extremely fine fibers and small voids, and is generally used for intermediate filtration and sound-absorbing functional layers. The hydroentangled process is to make the fibers intertangled by using high-pressure fine water needles, so that the material is flat and soft, and is used for synthetic leather base cloth.
[0003] The bicomponent spun-bonded hydroentangled process is to combine the composite spinning technology with the spun-bonded non-woven technology, and to peel off the composite filament fibers and intertangle them through the hydroentangled technology. The produced material can combine the technical advantages and performance advantages of the spun-bonded non-woven material and the hydroentangled non-woven material. However, the bicomponent spun-bonded hydroentangled process in the prior art still has some problems. For example, the bicomponent material is generally a hydrophobic material, and the prepared product has poor hydrophilic and moisture permeability. The hydrophilic modification treatment after the product is produced may cause the mechanical properties of the material to decrease. In the spun-bonded process, the smaller the fiber diameter is, the more likely the fiber is to break during the spinning process. Therefore, the fineness and the mechanical properties are difficult to balance.
[0004] In view of the above, it is of great significance to solve the above problems and prepare a bicomponent ultrafine spun-bonded hydroentangled non-woven material. SUMMARY
[0005] The present application aims to provide a bicomponent ultrafine spun-bonded hydroentangled non-woven material and a preparation method thereof, so as to solve the problems in the background art.
[0006] In order to solve the above technical problems, the present application provides the following technical scheme:
[0007] A preparation method of a bicomponent ultrafine spun-bonded hydroentangled non-woven material, comprising the following steps:
[0008] S1: uniformly mixing polyester masterbatch and modified polyester masterbatch, and drying to obtain PET masterbatch;
[0009] S2: uniformly mixing polyamide 6 masterbatch and modified polyamide 6 masterbatch, and drying to obtain PA-6 masterbatch:
[0010] S3: PET masterbatch and PA-6 masterbatch are sequentially added into the feeding port of the corresponding twin-screw extruder, melt-extruded, side-blowing air-drawing spun, laid, spunlace opened and reinforced, dried, and a bicomponent ultra-fine spunbonded water-jet nonwoven material is obtained.
[0011] Preferably, the mass ratio of the PET masterbatch and the PA6 masterbatch is 50-60:40-50.
[0012] More preferably, the mass ratio of the polyester masterbatch and the modified polyester masterbatch is 20:6-7; and the mass ratio of the polyamide 6 masterbatch and the modified polyamide 6 masterbatch is 20:6-7.
[0013] More preferably, the preparation method of the modified polyester masterbatch comprises the following steps: under a nitrogen atmosphere, dimethyl terephthalate, dimethyl 2,5-furan dicarboxylate, ethylene glycol, modified montmorillonite, zinc acetate, and ethylene glycol antimony are uniformly mixed, stirred at 180-200℃ for 2-3h, the temperature is increased to 260-270℃, and the pressure is reduced to 700-800Pa, stirred for 1-1.5h, the pressure is continuously reduced to 100-200Pa, and the stirring is continued for 3-4h, to obtain the modified polyester masterbatch.
[0014] More preferably, the modified polyester comprises the following raw materials in terms of mass fraction: 29-31 parts of dimethyl terephthalate, 3-3.1 parts of dimethyl 2,5-furan dicarboxylate, 15-16 parts of ethylene glycol, 10-12 parts of modified montmorillonite, 0.03-0.04 parts of zinc acetate, and 0.14-0.15 parts of ethylene glycol antimony.
[0015] More preferably, the preparation method of the modified montmorillonite comprises the following steps: (1) under a nitrogen atmosphere, styrene, maleic anhydride, N-methyldiallylamine, and azobisisobutyronitrile are uniformly mixed in isopentyl acetate and stirred at 70-80℃ for 6-8h, the product is centrifuged, washed, and dried to obtain a maleic anhydride copolymer;
[0016] (2) the maleic anhydride copolymer is added into a 35-40wt% sodium hydroxide solution, stirred at 30-40℃ for 40-60min, the pH is adjusted to 5-6, the solvent is removed by rotary evaporation, washed, and dried to obtain a hydrolyzed maleic anhydride copolymer;
[0017] (3) the hydrolyzed maleic anhydride copolymer and dibromoneopentyl glycol are uniformly mixed in ethanol, stirred at 65-70℃ for 48-72h, the solvent is removed by rotary evaporation, purified, and dried to obtain a quaternary ammonium hydrolyzed maleic anhydride copolymer;
[0018] (4) The montmorillonite is added into deionized water and uniformly dispersed by ultrasonic, and the quaternary ammonium hydrolyzed maleic anhydride copolymer is added, stirring at 60-65 DEG C for 2-3h, increasing the temperature to 70-75 DEG C for aging for 12-15h, centrifugation, washing, drying, to obtain the modified montmorillonite.
[0019] More preferably, the maleic anhydride copolymer comprises the following raw materials, by mass fraction: 5.1-5.3 parts of styrene, 4.8-5.0 parts of maleic anhydride, 2.7-2.9 parts of N-methyl diallylamine, 0.07-0.08 parts of azobisisobutyronitrile, 70-80 parts of isoamyl acetate;
[0020] The quaternary ammonium hydrolyzed maleic anhydride copolymer comprises the following raw materials, by mass fraction: 12-14 parts of hydrolyzed maleic anhydride copolymer, 6.5-6.6 parts of dibromoneopentyl glycol, 70-80 parts of ethanol;
[0021] The maleic anhydride copolymer comprises the following raw materials, by mass fraction: 4.5-5.5 parts of montmorillonite, 80-100 parts of deionized water, 9-10 parts of quaternary ammonium hydrolyzed maleic anhydride copolymer.
[0022] More preferably, the preparation method of the modified polyamide 6 master batch comprises the following steps: under the atmosphere of nitrogen, the caprolactam, 2,5-furan dicarboxylic acid, ethylenediamine and modified montmorillonite are uniformly mixed, and the mixture is stirred and reacted at 230-240 DEG C for 10-12h to obtain the modified polyamide 6 master batch.
[0023] More preferably, the modified polyamide 6 master batch comprises the following raw materials, by mass fraction: 44-46 parts of caprolactam, 3-3.4 parts of 2,5-furan dicarboxylic acid, 1.2-1.3 parts of ethylenediamine, 6-8 parts of modified montmorillonite.
[0024] More preferably, in the process of water jet opening and reinforcing, the water jet energy is 18-24J / g; in the process of side blowing traction spinning, the diameter of the bi-component fiber is 10-15μm, and the shape is hollow orange segment type; the areal density of the bi-component superfine spun-bonded water jet non-woven material is 100-120g / m 2 .
[0025] Compared with the prior art, the present application has the following beneficial effects: the present application prepares modified polyester master batch and modified polyamide 6 master batch by organic modification of montmorillonite as reinforcing filler, and uses the two as the corresponding modifiers of bi-component master batch, and prepares non-woven material composed of bi-component superfine fiber by spun-bonding method and water jet method, which has good mechanical properties and small diameter fineness, realizes the balance of fiber splitting ability and mechanical properties, and improves the hydrophilicity of the non-woven material.
[0026] The method for modifying the montmorillonite is as follows: under the initiation of azobisisobutyronitrile, styrene, maleic anhydride and N-methyldiallylamine are copolymerized to obtain a maleic anhydride copolymer, then the maleic anhydride copolymer is added into a sodium hydroxide solution to hydrolyze maleic anhydride groups in the copolymer, and the copolymer is acidified to obtain a hydrolyzed maleic anhydride copolymer containing carboxyl groups, further, the N-methyldiallylamine groups in the copolymer are quaternized by using dibromoneopentyl glycol, and the copolymer chains are introduced into the interlayer of the montmorillonite by using an intercalation method to obtain the modified montmorillonite.
[0027] The montmorillonite has a nanosheet layer structure and can interact with polymer chain ends to form a network structure, which helps to improve the mechanical properties of the fiber matrix after being introduced, and can also act as a thermal stabilizer to adsorb small molecules and water in the polymer, reducing thermal degradation of the material. Meanwhile, the montmorillonite can act as a nucleating agent to improve the crystallization rate and increase production efficiency. Using a styrene-maleic anhydride copolymer to modify the montmorillonite helps to improve its dispersibility in the matrix and improve the uniformity and mechanical properties of the fiber. In the process of traction spinning, the risk of accidental breakage can be reduced, so the fiber can have a smaller diameter. Further, the maleic anhydride groups are hydrolyzed by alkali to form carboxylate, further improving the hydrophilicity of the matrix. After adjusting the pH, a portion of the carboxyl groups remain in the system, which helps subsequent graft modification. By quaternizing the N-methyldiallylamine groups in the copolymer using dibromoneopentyl glycol, the two hydroxyl groups contained in the intercalated montmorillonite can further improve the hydrophilicity of the matrix.
[0028] The method for preparing the modified polyester is as follows: dimethyl terephthalate, dimethyl 2,5-furan dicarboxylate, ethylene glycol and the modified montmorillonite are subjected to ester exchange and polycondensation under the catalysis of zinc acetate and ethylene glycol antimony to obtain a modified polyester masterbatch. The method for preparing the modified nylon 6 masterbatch is as follows: caprolactam, 2,5-furan dicarboxylic acid, 1.2-1.3 parts of ethylenediamine and 6-8 parts of the modified montmorillonite are subjected to solid-phase polycondensation to obtain a modified nylon 6 masterbatch.
[0029] In the corresponding masterbatch, the similar structure introduced by copolymerization before use can further promote the dispersibility of the montmorillonite in the matrix and enhance the mechanical properties. Moreover, the grafting introduction can still contain a large number of hydrophilic groups, further ensuring the hydrophilicity of the matrix. Meanwhile, in the corresponding copolymerization modification process, furan groups are introduced, which helps to improve the mechanical properties of the fiber while making the two components have certain similarity, and the modified montmorillonite has a similar structure. Such design helps to improve the compatibility and adhesion of the two components, which is beneficial to prevent fiber splitting during spinning and improve the uniformity and mechanical properties of the fiber. However, the amount of the masterbatch prepared from the modified montmorillonite needs to be limited. If the content is too high, the adhesion of the two components will be large, the water jet opening efficiency will be reduced, and the water absorption of the material will be reduced. DETAILED DESCRIPTION
[0030] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.
[0031] It should be noted that the following parts are by weight, and the purchase manufacturers of all raw materials involved in the present application have no special restrictions. Exemplarily, the montmorillonite is calcium-based montmorillonite, which is produced in Chifeng City, Inner Mongolia Autonomous Region, has a cation exchange capacity of 110 mmol / 100 g, and a particle size of 200 mesh; the polyester masterbatch: PET, viscosity [ƞ]=0.65 dL·g -1 ; the polyamide 6 masterbatch: PA-6, [ƞ]=2.4 dL·g -1 ; the CAS number of styrene is 100-42-5; the CAS number of maleic anhydride is 108-31-6; the CAS number of N-methyldiallylamine is 2424-01-3; the CAS number of azobisisobutyronitrile is 78-67-1; the CAS number of isoamyl acetate is 123-92-2; the CAS number of dibromoneopentyl glycol is 3296-90-0; the CAS number of dimethyl terephthalate is 120-61-6; the CAS number of dimethyl 2,5-furandicarboxylate is 4282-32-0; the CAS number of ethylene glycol is 107-21-1; the CAS number of zinc acetate is 557-34-6; the CAS number of ethylene glycol antimony is 29736-75-2; the CAS number of caprolactam is 105-60-2; the CAS number of 2,5-furandicarboxylic acid is 3238-40-2; and the CAS number of ethylenediamine is 107-15-3.
[0032] In the following examples, parts are mass parts, and the above-mentioned and other raw materials used but not mentioned are commercially available; wherein, the surface density of the nonwoven material prepared in each example and the comparative example is 120 g / m 2 .
[0033] Example 1: The preparation method of the bicomponent ultrafine spunlaced hydroentangled nonwoven material includes the following steps:
[0034] Step one: preparation of modified montmorillonite: (1) under nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, 0.07 parts of azobisisobutyronitrile were added into 80 parts of isopentyl acetate and stirred uniformly, and then stirred at 75°C for 6h. The product was centrifuged, washed, and dried to obtain a maleic anhydride copolymer; (2) the maleic anhydride copolymer was added into 40wt% sodium hydroxide solution, stirred at 30°C for 60min, and the pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation, washed, and dried to obtain a hydrolyzed maleic anhydride copolymer; (3) 13 parts of the hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added into 80 parts of ethanol and stirred uniformly at 65°C for 72h. The solvent was removed by rotary evaporation, purified, and dried to obtain a quaternary ammonium hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite was uniformly dispersed in 100 parts of deionized water, and 9.5 parts of the quaternary ammonium hydrolyzed maleic anhydride copolymer was added. Stirring was carried out at 60°C for 2h, and then the temperature was increased to 70°C for aging for 12h. The product was centrifuged, washed, and dried to obtain modified montmorillonite;
[0035] Step two: preparation of modified polyester masterbatch: under nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of ethylene glycol antimony were mixed uniformly, and then stirred at 180°C for 2.5h. The temperature was increased to 260°C, and the pressure was decreased to 800Pa. Stirring was carried out for 1.5h, and then the pressure was continuously decreased to 200Pa. Stirring was continued for 3h to obtain a modified polyester masterbatch;
[0036] Step three: preparation of modified nylon 6 masterbatch: under nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine, and 7 parts of modified montmorillonite were mixed uniformly, and then stirred at 240°C for 12h to obtain a modified nylon 6 masterbatch;
[0037] Step four: preparation of bicomponent ultrafine spunbonded water-jet nonwoven material:
[0038] S1: the polyester masterbatch and the modified polyester masterbatch were mixed uniformly at a mass ratio of 20:7, and then dried to obtain a PET masterbatch;
[0039] S2: the nylon 6 masterbatch and the modified nylon 6 masterbatch were mixed uniformly at a mass ratio of 20:7, and then dried to obtain a PA-6 masterbatch:
[0040] S3: PET masterbatch and PA-6 masterbatch were added into the feeding port of the corresponding twin-screw extruder in a ratio of 50:50, the heating temperature of each zone of the PET masterbatch was 275℃, 280℃, 285℃, 285℃, 290℃, 290℃, and the heating temperature of each zone of the PA-6 masterbatch was 250℃, 255℃, 255℃, 260℃, 260℃, 260℃, and then they were melt-extruded, cooled by side blowing at a temperature of 25℃ and a wind speed of 1m / s, spun by traction, and formed into bi-component fibers with a diameter of 12μm, which were directly laid on a web, opened and reinforced by water jet with a water jet energy of 24J / g, dried, and obtained a bi-component ultra-fine spunbonded water-jet nonwoven material.
[0041] Example 2: The preparation method of the bi-component ultra-fine spunbonded water-jet nonwoven material comprises the following steps:
[0042] Step one: preparation of modified montmorillonite: (1) under a nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile were added into 80 parts of isoamyl acetate and stirred uniformly, and then reacted at 75℃ for 6h, and then the product was centrifuged, washed, and dried to obtain a maleic anhydride copolymer; (2) the maleic anhydride copolymer was added into a 40wt% sodium hydroxide solution, stirred at 30℃ for 60min, and then the pH was adjusted to 5.5±0.1, and then the solvent was removed by rotary evaporation, washed, and dried to obtain a hydrolyzed maleic anhydride copolymer; (3) 13 parts of the hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added into 80 parts of ethanol and stirred uniformly, and then reacted at 65℃ for 72h, and then the solvent was removed by rotary evaporation, purified, and dried to obtain a quaternary ammonium hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite was uniformly dispersed in 100 parts of deionized water by ultrasonic, and then 9.5 parts of the quaternary ammonium hydrolyzed maleic anhydride copolymer was added, stirred at 60℃ for 2h, and then the temperature was increased to 70℃ for aging for 12h, and then centrifuged, washed, and dried to obtain a modified montmorillonite;
[0043] Step two: preparation of modified polyester masterbatch: under a nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of ethylene glycol antimony were mixed uniformly, and then stirred at 180℃ for 2.5h, and then the temperature was increased to 260℃ and the pressure was reduced to 800Pa, and then stirred for 1.5h, and then the pressure was continuously reduced to 200Pa and stirred for 3h to obtain a modified polyester masterbatch;
[0044] Step three: preparation of modified nylon 6 masterbatch: under a nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine, and 7 parts of modified montmorillonite were mixed uniformly, and then reacted at 240℃ for 12h to obtain a modified nylon 6 masterbatch;
[0045] Step four: preparation of the bicomponent ultrafine spunbonded water-jet nonwoven material
[0046] S1: uniformly mix the polyester masterbatch and the modified polyester masterbatch in a mass ratio of 20:6, dry, and obtain a PET masterbatch;
[0047] S2: uniformly mix the polyamide 6 masterbatch and the modified polyamide 6 masterbatch in a mass ratio of 20:6, dry, and obtain a PA-6 masterbatch:
[0048] S3: sequentially add the PET masterbatch and the PA-6 masterbatch into the feeding port of the corresponding twin-screw extruder in a ratio of 50:50, the heating temperature of each zone of the PET masterbatch is 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, the heating temperature of each zone of the PA-6 masterbatch is 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, melt extrude, cool with side blowing at a temperature of 25℃ and a wind speed of 1m / s, draw spin, form bicomponent fibers with a diameter of 12μm, directly lay the fibers, water-jet, open and reinforce at a water-jet energy of 24J / g, dry, and obtain the bicomponent ultrafine spunbonded water-jet nonwoven material.
[0049] Example 3: the preparation method of the bicomponent ultrafine spunbonded water-jet nonwoven material includes the following steps:
[0050] Step one: preparation of the modified montmorillonite: (1) under a nitrogen atmosphere, uniformly stir 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile in 80 parts of isoamyl acetate, and react at 75℃ for 6h, centrifuge, wash, and dry to obtain a maleic anhydride copolymer; (2) add the maleic anhydride copolymer into a 40wt% sodium hydroxide solution, stir at 30℃ for 60min, adjust the pH to 5.5±0.1, and remove the solvent by rotary evaporation, wash, and dry to obtain a hydrolyzed maleic anhydride copolymer; (3) uniformly stir 13 parts of the hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol in 80 parts of ethanol, stir at 65℃ for 72h, remove the solvent by rotary evaporation, purify, and dry to obtain a quaternary ammonium hydrolyzed maleic anhydride copolymer; (4) uniformly ultrasonic disperse 5 parts of montmorillonite in 100 parts of deionized water, add 9.5 parts of the quaternary ammonium hydrolyzed maleic anhydride copolymer, stir at 60℃ for 2h, increase the temperature to 70℃ and age for 12h, centrifuge, wash, and dry to obtain the modified montmorillonite;
[0051] Step two: preparation of modified polyester masterbatch: under nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furan dicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, 0.14 parts of ethylene glycol antimony are mixed uniformly, stirred at 180℃ for 2.5h, the temperature is increased to 260℃, and the pressure is reduced to 800Pa, stirred for 1.5h, the pressure is continuously reduced to 200Pa, and stirred for 3h, to obtain the modified polyester masterbatch;
[0052] Step three: preparation of modified nylon 6 masterbatch: under nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furan dicarboxylic acid, 1.2 parts of ethylenediamine, 7 parts of modified montmorillonite are mixed uniformly, and stirred at 240℃ for 12h to obtain the modified nylon 6 masterbatch;
[0053] Step four: preparation of bicomponent ultrafine spunbonded water-jet nonwoven material:
[0054] S1: the polyester masterbatch and the modified polyester masterbatch are mixed uniformly in a mass ratio of 20:7, dried, and the PET masterbatch is obtained;
[0055] S2: the nylon 6 masterbatch and the modified nylon 6 masterbatch are mixed uniformly in a mass ratio of 20:7, dried, and the PA-6 masterbatch is obtained:
[0056] S3: the PET masterbatch and the PA-6 masterbatch are added into the corresponding twin-screw extruder feeding port in a ratio of 60:40, the heating temperature of each zone of the PET masterbatch is 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively, the heating temperature of each zone of the PA-6 masterbatch is 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively, melt extrusion, cooled by side blowing with a temperature of 25℃ and a wind speed of 1m / s, spun by traction, formed into bicomponent fibers with a diameter of 12μm, directly laid, opened and reinforced by water-jet with a water-jet energy of 24J / g, dried, and the bicomponent ultrafine spunbonded water-jet nonwoven material is obtained.
[0057] Comparative example 1: based on example 1, the montmorillonite is only modified by cetyltrimethylammonium bromide, and the rest of the process remains unchanged, as shown in the following steps:
[0058] Step one: preparation of modified montmorillonite: 5 parts of montmorillonite are added to 100 parts of deionized water and ultrasonically dispersed uniformly, 3 parts of cetyltrimethylammonium bromide are added, stirred at 60℃ for 2h, heated to 70℃ and aged for 12h, centrifuged, washed, and dried to obtain the modified montmorillonite;
[0059] Step two: preparation of modified polyester masterbatch: under nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furan dicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, 0.14 parts of ethylene glycol antimony are mixed uniformly, stirred at 180℃ for 2.5h, the temperature is increased to 260℃, and the pressure is reduced to 800Pa, stirred for 1.5h, the pressure is continuously reduced to 200Pa, and stirred for 3h, to obtain the modified polyester masterbatch;
[0060] Step three: preparation of modified nylon 6 masterbatch: under nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furan dicarboxylic acid, 1.2 parts of ethylenediamine, 7 parts of modified montmorillonite are mixed uniformly, and stirred at 240℃ for 12h to obtain the modified nylon 6 masterbatch;
[0061] Step four: preparation of bicomponent ultrafine spunbonded water-jet nonwoven material:
[0062] S1: the polyester masterbatch and the modified polyester masterbatch are mixed uniformly in a mass ratio of 20:7, dried, and the PET masterbatch is obtained;
[0063] S2: the nylon 6 masterbatch and the modified nylon 6 masterbatch are mixed uniformly in a mass ratio of 20:7, dried, and the PA-6 masterbatch is obtained:
[0064] S3: the PET masterbatch and the PA-6 masterbatch are added into the corresponding twin-screw extruder feeding port in a ratio of 50:50, the heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃ respectively, the heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃ respectively, melt extrusion, cooling by side blowing with a temperature of 25℃ and a wind speed of 1m / s, drawing spinning, forming bicomponent fibers with a diameter of 12μm, directly laying web, water-jet opening and reinforcing with a water-jet energy of 24J / g, drying, to obtain the bicomponent ultrafine spunbonded water-jet nonwoven material.
[0065] Comparative example 2: based on example 1, the addition amount of modified polyester masterbatch and modified nylon 6 masterbatch is increased, and the rest of the process remains unchanged, as shown in the following steps:
[0066] Step one: preparation of modified montmorillonite: (1) under nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, 0.07 parts of azobisisobutyronitrile were added into 80 parts of isopentyl acetate and stirred uniformly, and then stirred at 75℃ for 6h. The product was centrifuged, washed, and dried to obtain a maleic anhydride copolymer; (2) the maleic anhydride copolymer was added into 40wt% sodium hydroxide solution, stirred at 30℃ for 60min, and the pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation, washed, and dried to obtain a hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added into 80 parts of ethanol and stirred uniformly at 65℃ for 72h. The solvent was removed by rotary evaporation, purified, and dried to obtain a quaternary ammonium hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite was uniformly dispersed in 100 parts of deionized water, and 9.5 parts of quaternary ammonium hydrolyzed maleic anhydride copolymer was added. Stirring was carried out at 60℃ for 2h, and then the temperature was increased to 70℃ for aging for 12h. The product was centrifuged, washed, and dried to obtain modified montmorillonite;
[0067] Step two: preparation of modified polyester masterbatch: under nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of ethylene glycol antimony were mixed uniformly, and then stirred at 180℃ for 2.5h. The temperature was increased to 260℃, and the pressure was decreased to 800Pa. Stirring was carried out for 1.5h, and then the pressure was continuously decreased to 200Pa. Stirring was continued for 3h to obtain a modified polyester masterbatch;
[0068] Step three: preparation of modified nylon 6 masterbatch: under nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine, and 7 parts of modified montmorillonite were mixed uniformly, and then stirred at 240℃ for 12h to obtain a modified nylon 6 masterbatch;
[0069] Step four: preparation of bicomponent ultrafine spunbonded water-jet nonwoven material:
[0070] S1: the polyester masterbatch and the modified polyester masterbatch were mixed uniformly at a mass ratio of 20:12, and then dried to obtain a PET masterbatch;
[0071] S2: the nylon 6 masterbatch and the modified nylon 6 masterbatch were mixed uniformly at a mass ratio of 20:12, and then dried to obtain a PA-6 masterbatch:
[0072] S3: PET masterbatch and PA-6 masterbatch were added into the feeding port of the corresponding twin-screw extruder in a ratio of 50:50, the heating temperature of each zone of the PET masterbatch was 275℃, 280℃, 285℃, 285℃, 290℃, 290℃, and the heating temperature of each zone of the PA-6 masterbatch was 250℃, 255℃, 255℃, 260℃, 260℃, 260℃, melt extrusion, cooled by side blowing with a temperature of 25℃ and a wind speed of 1m / s, spunlaid to form a bi-component fiber with a diameter of 12μm, directly laid, opened and reinforced by water jet with a water jet energy of 24J / g, dried to obtain a bi-component ultra-fine spunbonded water jet nonwoven material.
[0073] Comparative Example 3: Based on Example 1, no 2,5-furandicarboxylic acid dimethyl ester was added in the preparation of the modified polyester masterbatch, and the rest of the process remained unchanged, as shown in the following steps:
[0074] Step one: preparation of modified montmorillonite: (1) under nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, 0.07 parts of azobisisobutyronitrile were added into 80 parts of isoamyl acetate and stirred uniformly, and stirred at 75℃ for 6h, centrifuged, washed and dried to obtain maleic anhydride copolymer; (2) the maleic anhydride copolymer was added into 40wt% sodium hydroxide solution, stirred at 30℃ for 60min, adjusted pH to 5.5±0.1, removed the solvent by rotary evaporation, washed and dried to obtain hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added into 80 parts of ethanol and stirred uniformly, stirred at 65℃ for 72h, removed the solvent by rotary evaporation, purified and dried to obtain quaternary ammonium hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite was added into 100 parts of deionized water and ultrasonically dispersed uniformly, 9.5 parts of quaternary ammonium hydrolyzed maleic anhydride copolymer was added, stirred at 60℃ for 2h, increased the temperature to 70℃ and aged for 12h, centrifuged, washed and dried to obtain modified montmorillonite;
[0075] Step two: preparation of modified polyester masterbatch: under nitrogen atmosphere, 33.05 parts of terephthalic acid dimethyl ester, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, 0.14 parts of ethylene glycol antimony were mixed uniformly, stirred at 180℃ for 2.5h, increased the temperature to 260℃ and reduced the pressure to 800Pa, stirred for 1.5h, continued to reduce the pressure to 200Pa and continued to stir for 3h to obtain modified polyester masterbatch;
[0076] Step three: preparation of modified nylon 6 masterbatch: under nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine, 7 parts of modified montmorillonite were mixed uniformly, stirred at 240℃ for 12h to obtain modified nylon 6 masterbatch;
[0077] Step four: preparation of the bicomponent ultrafine spunbonded water-jet nonwoven material
[0078] S1: uniformly mix the polyester masterbatch and the modified polyester masterbatch at a mass ratio of 20:7, dry, and obtain a PET masterbatch;
[0079] S2: uniformly mix the polyamide 6 masterbatch and the modified polyamide 6 masterbatch at a mass ratio of 20:7, dry, and obtain a PA-6 masterbatch:
[0080] S3: sequentially add the PET masterbatch and the PA-6 masterbatch into the feeding port of the corresponding twin-screw extruder at a ratio of 50:50, the heating temperature of each zone of the PET masterbatch is 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, the heating temperature of each zone of the PA-6 masterbatch is 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, melt extrude, cool with side blowing at a temperature of 25℃ and a wind speed of 1m / s, draw spin, form bicomponent fibers with a diameter of 12μm, directly lay the fibers, water-jet, open and reinforce at a water-jet energy of 24J / g, dry, and obtain the bicomponent ultrafine spunbonded water-jet nonwoven material.
[0081] Comparative Example 4: based on Example 1, do not add 2,5-furandicarboxylic acid in the preparation of the modified polyamide masterbatch, and the rest of the process remains unchanged, which is shown in the following steps:
[0082] Step one: preparation of the modified montmorillonite: (1) under a nitrogen atmosphere, uniformly stir 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile in 80 parts of isoamyl acetate, and react at 75℃ for 6h, centrifuge, wash, and dry to obtain a maleic anhydride copolymer; (2) add the maleic anhydride copolymer into a 40wt% sodium hydroxide solution, stir at 30℃ for 60min, adjust the pH to 5.5±0.1, and remove the solvent by rotary evaporation, wash, and dry to obtain a hydrolyzed maleic anhydride copolymer; (3) uniformly stir 13 parts of the hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol in 80 parts of ethanol, stir at 65℃ for 72h, remove the solvent by rotary evaporation, purify, and dry to obtain a quaternary ammonium hydrolyzed maleic anhydride copolymer; (4) uniformly ultrasonic disperse 5 parts of montmorillonite in 100 parts of deionized water, add 9.5 parts of the quaternary ammonium hydrolyzed maleic anhydride copolymer, stir at 60℃ for 2h, increase the temperature to 70℃ and age for 12h, centrifuge, wash, and dry to obtain the modified montmorillonite;
[0083] Step two: preparation of modified polyester masterbatch: under the atmosphere of nitrogen, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, 0.14 parts of ethylene glycol antimony are mixed uniformly, stirred at 180℃ for 2.5h, the temperature is increased to 260℃, and the pressure is reduced to 800Pa, stirred for 1.5h, the pressure is continuously reduced to 200Pa, and stirred for 3h, to obtain the modified polyester masterbatch;
[0084] Step three: preparation of modified nylon 6 masterbatch: under the atmosphere of nitrogen, 45 parts of caprolactam, 3.3 parts of adipic acid, 1.2 parts of ethylenediamine, 7 parts of modified montmorillonite are mixed uniformly, and stirred at 240℃ for 12h to obtain the modified nylon 6 masterbatch;
[0085] Step four: preparation of bicomponent ultrafine spunbonded water-jet nonwoven material:
[0086] S1: the polyester masterbatch and the modified polyester masterbatch are mixed uniformly at a mass ratio of 20:7, dried, and the PET masterbatch is obtained;
[0087] S2: the nylon 6 masterbatch and the modified nylon 6 masterbatch are mixed uniformly at a mass ratio of 20:7, dried, and the PA-6 masterbatch is obtained:
[0088] S3: the PET masterbatch and the PA-6 masterbatch are added into the corresponding twin-screw extruder feeding port in a ratio of 50:50, the heating temperature of each zone of the PET masterbatch is 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, the heating temperature of each zone of the PA-6 masterbatch is 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, melt extrusion, cooled by side blowing at a temperature of 25℃ and a wind speed of 1m / s, spun by traction, formed into bicomponent fibers with a diameter of 12μm, directly laid, opened and reinforced by water-jet at a water-jet energy of 24J / g, dried, and the bicomponent ultrafine spunbonded water-jet nonwoven material is obtained.
[0089] Performance test: (1) the tensile properties of the samples prepared in each example and the comparative example are tested according to GB / T 24218.3-2010 using a universal material testing machine; wherein the sample length is 30cm, the width is 5cm, and the tensile rate is 100m / min; (2) the tear properties of the samples prepared in each example and the comparative example are tested according to GB / T 3917.2-2009 using a universal material testing machine; wherein the sample length is 30cm, the width is 5cm, and the tensile rate is 100m / min; (3) the water absorption properties of each example and the comparative example are tested according to GB / T 21655.1-2023; wherein the sample length is 10cm, and the width is 10cm. The experimental data is shown in the following table.
[0090]
[0091] Conclusion: As can be seen from the table, the modified polyester masterbatch and the modified nylon 6 masterbatch are prepared by using montmorillonite as the reinforcing filler based on organic modification, and the non-woven material composed of double-component ultra-fine fibers is prepared by using the double-component masterbatch as the corresponding modifier through the spunbonding method and the water jet method, which has good mechanical properties and small diameter fineness, realizes the balance of fiber splitting ability and mechanical properties, and improves the hydrophilicity of the non-woven material.
[0092] In the comparative example 1, the montmorillonite is only modified by using cetyltrimethylammonium bromide, and has weak dispersing performance and lacks reinforcing segments and hydrophilic groups, so the mechanical properties are greatly reduced, and the absorption time is long; in the comparative example 2, the addition amount of the modified polyester masterbatch and the modified nylon 6 masterbatch is increased, the adhesion between the double components is large, the water jet opening efficiency is reduced, and the water absorption performance of the material is reduced; in the comparative examples 3 and 4, the furan groups are not introduced into the single modified masterbatch, the similarity between the double components is reduced, the compatibility and adhesion are reduced, the fibers are split during spinning, the uniformity of the fibers is reduced, and the mechanical properties are slightly reduced.
[0093] Finally, it should be pointed out that: the above only describes the preferred embodiments of the present application and is not used to limit the present application, although the present application has been described in detail with reference to the foregoing embodiments, for those skilled in the art, the technical solutions recorded in the foregoing embodiments can still be modified, or some technical features can be replaced equivalently. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. A method of making a bicomponent microspun spunbonded hydroentangled nonwoven material, characterized in that, It comprises the following steps: S1: mix the polyester masterbatch and modified polyester masterbatch uniformly, dry, and obtain PET masterbatch; S2: mix the polyamide 6 masterbatch and modified polyamide 6 masterbatch uniformly, dry, and obtain PA-6 masterbatch: S3: add the PET masterbatch and PA-6 masterbatch into the feeding port of the corresponding twin-screw extruder in sequence, melt extrude, side-blowing air traction spin, lay-up, water jet fiberization reinforcement, dry, and obtain the bicomponent ultra-fine spunbonded water jet nonwoven material; The ratio of the PET masterbatch and PA-6 masterbatch is 50-60:40-50. The modified polyester comprises the following raw materials in parts by mass: 29-31 parts of dimethyl terephthalate, 3-3.1 parts of dimethyl 2,5-furandicarboxylate, 15-16 parts of ethylene glycol, 10-12 parts of modified montmorillonite, 0.03-0.04 parts of zinc acetate, and 0.14-0.15 parts of ethylene glycol antimony. The modified polyamide 6 masterbatch comprises the following raw materials in parts by mass: 44-46 parts of caprolactam, 3-3.4 parts of 2,5-furandicarboxylic acid, 1.2-1.3 parts of ethylenediamine, and 6-8 parts of modified montmorillonite. The preparation method of the modified montmorillonite comprises the following steps: (1) under a nitrogen atmosphere, stir styrene, maleic anhydride, N-methyldiallylamine, and azobisisobutyronitrile in isoamyl acetate uniformly, stir at 70-80℃ for 6-8h, centrifuge, wash, and dry to obtain a maleic anhydride copolymer; (2) add the maleic anhydride copolymer into a 35-40wt% sodium hydroxide solution, stir at 30-40℃ for 40-60min, adjust the pH to 5-6, remove the solvent by rotary evaporation, wash, and dry to obtain a hydrolyzed maleic anhydride copolymer; (3) stir the hydrolyzed maleic anhydride copolymer and dibromoneopentyl glycol in ethanol uniformly, stir at 65-70℃ for 48-72h, remove the solvent by rotary evaporation, purify, and dry to obtain a quaternized hydrolyzed maleic anhydride copolymer; (4) ultrasonically disperse montmorillonite in deionized water uniformly, add the quaternized hydrolyzed maleic anhydride copolymer, stir at 60-65℃ for 2-3h, raise the temperature to 70-75℃ for aging for 12-15h, centrifuge, wash, and dry to obtain the modified montmorillonite.
2. The method of claim 1, wherein the bicomponent microspun spunbonded hydroentangled nonwoven material is prepared by the steps of: The maleic anhydride copolymer comprises the following raw materials in parts by mass: 5.1-5.3 parts of styrene, 4.8-5.0 parts of maleic anhydride, 2.7-2.9 parts of N-methyldiallylamine, 0.07-0.08 parts of azobisisobutyronitrile, and 70-80 parts of isoamyl acetate; The quaternized hydrolyzed maleic anhydride copolymer comprises the following raw materials in parts by mass: 12-14 parts of the hydrolyzed maleic anhydride copolymer, 6.5-6.6 parts of dibromoneopentyl glycol, and 70-80 parts of ethanol; The maleic anhydride copolymer comprises the following raw materials in parts by mass: 4.5-5.5 parts of montmorillonite, 80-100 parts of deionized water, and 9-10 parts of the quaternized hydrolyzed maleic anhydride copolymer.
3. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 1, characterized in that: The mass ratio of the polyester masterbatch and modified polyester masterbatch is 20:6-7, and the mass ratio of the polyamide 6 masterbatch and modified polyamide 6 masterbatch is 20:6-7.
4. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 1, characterized in that: The preparation method of the modified polyester master batch comprises the following steps: under a nitrogen atmosphere, dimethyl terephthalate, dimethyl 2,5-furan dicarboxylate, ethylene glycol, modified montmorillonite, zinc acetate and ethylene glycol antimony are uniformly mixed, stirring at 180-200 DEG C for 2-3h, increasing the temperature to 260-270 DEG C, and reducing the pressure to 700-800 Pa, stirring for 1-1.5h, continuously reducing the pressure to 100-200 Pa, and continuously stirring for 3-4h to obtain the modified polyester master batch.
5. The method of claim 1, wherein the bicomponent microspun spunbonded hydroentangled nonwoven material is characterized by: The preparation method of the modified nylon 6 master batch comprises the following steps: under a nitrogen atmosphere, caprolactam, 2,5-furan dicarboxylic acid and ethylenediamine are uniformly mixed, and stirring reaction is carried out at 230-240 DEG C for 10-12h to obtain the modified nylon 6 master batch.
6. The method of claim 1, wherein the bicomponent microspun spunbonded hydroentangled nonwoven material is characterized by: The water jet energy is 18-24 J / g in the water jet opening and reinforcing process; the diameter of the bicomponent fiber is 10-15 μm and the shape is hollow orange segment type in the side blowing and drawing spinning process; the surface density of the bicomponent ultrafine spun-bonded water jet nonwoven material is 100-120 g / m 2 .
7. The bicomponent microspun spunbonded hydroentangled nonwoven material prepared by the method according to any one of claims 1-6.
Citation Information
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