CN113279149A - Preparation method of polyamide superfine fiber non-woven two-dimensional film and two-dimensional film - Google Patents
Preparation method of polyamide superfine fiber non-woven two-dimensional film and two-dimensional film Download PDFInfo
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- CN113279149A CN113279149A CN202110373663.8A CN202110373663A CN113279149A CN 113279149 A CN113279149 A CN 113279149A CN 202110373663 A CN202110373663 A CN 202110373663A CN 113279149 A CN113279149 A CN 113279149A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—Polyamides
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
Abstract
The invention provides a preparation method of a thermoplastic polyamide superfine fiber non-woven two-dimensional film and the two-dimensional film. The invention comprises the following steps: 1) taking a caprolactam monomer, adding an initiator, and melting to obtain a raw material A; 2) taking caprolactam monomer, adding a catalyst, and melting to obtain a raw material B; 3) mixing the raw material A and the raw material B at a temperature of 80-200 ℃ in a fluid mixing part of a device; 4) and further inputting the mixture into a spinning device equipped with a high-voltage electrostatic field, spinning at a voltage of 5-40 KV, stretching under an electric field and an air field to form superfine fibers, and collecting random lapping of the superfine fibers on a receiving device to obtain the two-dimensional porous membrane. The superfine fiber non-woven two-dimensional film is obtained by the one-step method, the preparation process is simple, the operation is convenient, the spinning temperature is low, the bonding between fibers is avoided, a non-monomer organic solvent is not used, and the spinning of a conventional linear thermoplastic polymer and the generation of a two-dimensional film structure are realized.
Description
Technical Field
The invention relates to the technical field of porous membranes, in particular to a preparation method of a polyamide superfine fiber non-woven two-dimensional membrane and the two-dimensional membrane.
Background
In general, the chemical fiber industry and the downstream two-dimensional cloth or film material forming process are separate and independent processes and are also separate business businesses. The spinning of fiber is to use polymer with higher molecular weight as raw material, and obtain filament or staple fiber through melt spinning, solution spinning and other processes, and the fiber size (diameter) is usually above 10 microns. Smaller scale (diameter) fibers are not achievable with conventional techniques and equipment due to the high melt or solution viscosity of the polymer; the formation of a two-dimensional structure (cloth or film) typically requires a separate downstream weaving or other forming process. In the field of nonwoven material production, such as spunbonding and meltblowing, the spinning of fibers and the web formation of the material are carried out in one step, but it is also necessary that the starting material is a polymer of relatively high molecular weight which has already been polymerized and whose fiber fineness can be as fine as several micrometers to tens of micrometers. Lower scale (nano-scale) fibers are typically achieved by electrospinning techniques using lower viscosity polymer solutions (about 1-20% solids), where electrostatic fields of high voltage are used as the driving force for fiber drawing, and the process requires low fluid viscosity and easy drawing, in addition to high voltages of 5-40 kv. Therefore, the polymer is usually dissolved in an organic solvent to form a 1 to 20% solution as an electrospinning raw material. The process requires that a large amount of organic solvent is used, so that the yield of the fiber is greatly reduced, the process cost is greatly increased, the consequences of solvent recovery and environmental pollution are brought, and the process is a great obstacle to further industrialization of the technology. Therefore, obtaining superfine fiber in a way of not volatilizing solvent has been a long difficulty in industry.
At present, the solvent-free electrospinning technology can be mainly divided into two types, i.e., melt electrospinning and reaction-solidification electrospinning. Among them, the research on melt electrospinning is relatively extensive, but there is no currently recognized mature apparatus in which the key raw material is a linear thermoplastic polymer, the required raw material requirement is a polymer that has been polymerized, the process temperature is above the melting point of the polymer, and the melt viscosity is high, so that it is difficult to obtain ultrafine fibers under an electrostatic field. In addition, the cooling speed of the high-temperature melt jet flow also restricts the fiber forming speed, and the process is very easy to cause that the raw materials are not completely cooled and solidified after the jet flow is deposited in the manufacturing process, thereby causing the bonding between fibers and influencing the fiber form. In recent years, researchers have reported a novel reactive solidification type electrostatic spinning, wherein reactive solidification refers to that molten polymer prepolymer is used as spinning precursor liquid, rapid polymerization reaction is induced by various modes in the electrostatic spinning process, most of the molten polymer prepolymer can finish jet solidification, and no solvent is volatilized in the spinning process. However, the systems disclosed in the novel reactive curing electrospinning technology are generally thermosetting crosslinking systems (such as epoxy resins) or acrylic acid derivatives containing double bond components capable of being crosslinked by ultraviolet light, and the crosslinked products are thermosetting materials with high brittleness and poor tensile and fiber properties.
Chinese patent CN107974717A discloses a conjugated two-component solvent-free electrospun micro-nanofiber and a preparation method and a device thereof in 2018, 5.1.A preparation method comprises the steps of firstly preparing an oxidation component spinning precursor solution containing a vinyl active monomer, a toughening resin and an oxidation component and a reduction component spinning precursor solution containing a vinyl active monomer, a toughening resin and a reduction component, then respectively injecting the oxidation component spinning precursor solution and the reduction component spinning precursor solution into a liquid storage mechanism of an electrospinning device, and carrying out electrostatic spinning under the action of electric field force to obtain a micro-nanofiber membrane. In the preparation method, no or only a small amount of raw materials volatilize, most of the raw materials participate in curing to form fibers, the utilization rate of the raw materials is effectively improved, and the utilization rate of the raw materials is over 90 percent. However, as mentioned above, this electrospinning method is limited to the reaction of thermosetting crosslinked resin, and the properties of the obtained material belong to crosslinked materials; this is a substantial difference in chemical structure from the linear thermoplastic polymers used in conventional fiber spinning for industrial applications, and the fiber properties of such materials are relatively poor.
Disclosure of Invention
The invention aims to provide a preparation method of a thermoplastic polyamide superfine fiber non-woven two-dimensional film and a two-dimensional film material, and aims to solve the problems that in the prior art, the raw material requirements of a melt electrostatic spinning process are high polymers which are polymerized, the spinning temperature is high, the operation is inconvenient due to cooling during jet flow deposition, the fiber morphology is influenced by bonding between fibers, and a reaction curing type electrostatic spinning process needs to use active monomers which can be cured into fibers, so that the reaction of the reaction curing type electrostatic spinning process is limited to thermosetting crosslinking resin and cannot be applied to the spinning of conventional linear thermoplastic polymers.
In order to solve the technical problem, the technical scheme of the invention is realized as follows:
in one aspect, the invention provides a method for preparing a polyamide superfine fiber non-woven two-dimensional film, which comprises the following steps: 1) taking a caprolactam monomer, adding an initiator, and melting to obtain a raw material A, wherein the molar ratio of the initiator to the caprolactam monomer is 1-10: 99-90; 2) taking caprolactam monomer, adding a catalyst, and melting to obtain a raw material B, wherein the molar ratio of the catalyst to the caprolactam monomer is 1-10: 99-90; 3) mixing the raw material A obtained in the step 1) and the raw material B obtained in the step 2) at 80-200 ℃ to obtain a mixture; 4) and (3) further inputting the mixture obtained in the step 3) into a spinning device equipped with a high-voltage electrostatic field, spinning in the electrostatic field and stretching under the electric field and the air field to form superfine fibers, wherein the voltage of the electrostatic field is 5-40 KV, and collecting random lapping of the superfine fibers on a receiving device to obtain the two-dimensional porous membrane.
The invention takes low viscosity caprolactam (monomer) above the melting point as the initial raw material, utilizes the anionic polymerization mechanism of the monomer under the action of the initiator and the catalyst to realize the simultaneous implementation of the mixing and polymerization reaction of low viscosity polymerizable monomer, the conversion of the polymerization reaction into certain high molecular weight molten fluid, the fluid spinning and stretching, the high molecular crystallization and the electrostatic field force drafting forming, and obtains the superfine fiber non-woven two-dimensional film by one-step method. The preparation method of the invention does not use non-monomer organic solvent, has no yield and cost loss caused by solvent volatilization, does not bring the consequences of solvent recovery and environmental pollution, completes nearly 100 percent of polymerization and spinning lapping conversion, realizes electrostatic spinning of conventional linear thermoplastic polymer, and obtains the nano-scale to micron-scale superfine fiber non-woven two-dimensional film.
In the invention, caprolactam monomer in raw material A reacts with an initiator in a liquid state to generate caprolactam-blocked isocyanate, and caprolactam monomer in raw material B reacts with a catalyst to generate caprolactam anion; after the raw material A and the raw material B are mixed, the caprolactam-blocked isocyanate has an imide structure and has strong hydrophilic property, so that the caprolactam-blocked isocyanate is easily attacked by caprolactam anions and subjected to a ring opening reaction to generate another active anion, and the caprolactam reacts with the active anion to generate active caprolactam isocyanate so as to realize chain growth; then, the caprolactam is attacked by caprolactam anion to open the ring, and the circulation is continued; the melt viscosity is continuously increased along with the increase of the polymerization degree, when the polymerization reaction is carried out to a viscosity range suitable for spinning (namely the conversion rate of a polymerization reaction monomer is 40-60%), the melt is placed under the voltage of 5-40 KV for spinning and is stretched under an electric field and an air field to form superfine fibers, and random lapping of the superfine fibers is collected on a receiving device to obtain the two-dimensional porous membrane.
In a preferred embodiment, the catalyst is any one of sodium hydride, potassium hydride and lithium hydride. Because the moisture is the biggest obstacle of the caprolactam anion ring-opening polymerization reaction for preparing the nylon material, the invention adopts hydride as the catalyst, does not generate moisture in the reaction process, avoids the influence of the moisture on the caprolactam anion ring-opening polymerization reaction, and simultaneously does not need vacuum dehydration in the caprolactam anion ring-opening polymerization reaction process.
In a preferred embodiment, the catalyst is suspended in mineral oil, and the content of the catalyst in the mineral oil is 20-80%. Because the hydride catalyst of the invention is very active in property, for the sake of safety, and meanwhile, from the viewpoint of controlling the polymerization reaction speed, the catalyst is suspended in mineral oil in advance, and the catalyst is convenient to use, convenient to store and good in service performance.
As a preferred embodiment, the initiator is any one of TDI, MDI, IPDI, HMDI, HDI, LDI. The initiator is isocyanate capable of forming an open-ring imide structure with a caprolactam monomer, and comprises Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI) and the like.
As a preferred embodiment, the caprolactam monomer is dried in a vacuum drying oven at 55-65 ℃ for 20-30 h before use to remove the contained moisture. In the invention, the caprolactam monomer is dried in vacuum before use to remove the moisture in the caprolactam monomer, so as to fully ensure that no moisture is doped in the caprolactam anion ring-opening polymerization reaction process.
In a preferred embodiment, in the electrostatic spinning equipment, the needle head is connected with a positive high-voltage power supply, the voltage of the positive high-voltage power supply is 5-25 KV, the receiving device is connected with a negative high-voltage power supply, and the voltage of the negative high-voltage power supply is-5-15 KV. The invention adopts the mode that the needle is connected with the positive high voltage and the receiving device is connected with the negative high voltage, can regulate and control the potential difference of the high-voltage electric field in a wider range, obtains a wider-range jet drafting effect and improves the electrostatic spinning effect.
In a preferred embodiment, the horizontal distance between the needle and the receiving device is 15-20 cm. The electrostatic spinning equipment comprises a box body, wherein the box body can be set with temperature so as to fully ensure the spinning temperature; a needle head is arranged on one side of the box body, a receiving device is arranged on the other side of the box body, the receiving device is usually a receiving plate or a receiving roller, and the bottom of the receiving plate or the receiving roller is fixed in the box body through an insulating base; applying a DC high voltage power supply between the needle and the receiving device sufficient to cause electrospinning to form, the receiving plate receiving the random lapping of the superfine fibers in a static manner, the roller receiving the random lapping of the superfine fibers in a rotating manner, thereby forming a two-dimensional porous membrane with a certain thickness or surface density; the arrangement of the insulating base is simple and feasible.
In another aspect, the invention provides a polyamide ultrafine fiber non-woven two-dimensional film, which is prepared according to the preparation method of the polyamide ultrafine fiber non-woven two-dimensional film.
The polyamide is commonly called nylon, and the polycaprolactam of the invention is commonly called nylon 6. The nylon has the characteristics of toughness, wear resistance, self lubrication, wide use temperature range and the like, and becomes engineering plastic and fiber widely applied in the industry at present. Nylon 6 is one of the most prominent varieties. The chemical composition of the fibers in the non-woven two-dimensional film is polycaprolactam (nylon 6), the fibers are solid columnar fibers with smooth surfaces, the diameter of the solid columnar fibers is within the range of 100 nanometers to 10 micrometers, and the solid columnar fibers are laid in a random distribution mode to form the two-dimensional porous film. The non-woven two-dimensional membrane has the advantages of excellent mechanical and engineering properties of nylon 6, controllable fiber diameter and micropore size, and heat resistance superior to that of a conventional polyolefin porous membrane, and can be used in the fields of gas-liquid multiphase filtration, porous media and the like.
As a preferred embodiment, the non-woven two-dimensional film further comprises any one or more of a filler, an inert filler and a non-reactive functional component not participating in the above polymerization reaction, and the total addition amount of the filler, the inert filler and the non-reactive functional component not participating in the above polymerization reaction is not more than 10% of the total weight of the non-woven two-dimensional film. In the preparation process of the non-woven two-dimensional film, a filling agent, an inert filling material or a non-reactive functional component which does not participate in the polymerization reaction can be added into the formula of the raw material A or the raw material B, so that the comprehensive performance of the non-woven two-dimensional film is improved.
As a preferred embodiment, the filler is any one or more of a plasticizer, an antioxidant, an anti-aging agent and a toughening agent, and the inert filler is any one or more of talcum powder and quartz sand. The use of the fillers can improve the plasticity, the aging resistance and the toughness of the non-woven two-dimensional film; the strength and hardness of the non-woven two-dimensional film can be improved by adding inert fillers such as talcum powder, quartz sand and the like; the addition of non-reactive functional components that do not participate in the above polymerization reaction can enhance other functionalities of the nonwoven two-dimensional film, thereby further enhancing the overall performance of the nonwoven two-dimensional film.
Compared with the prior art, the invention has the beneficial effects that: the invention takes low-viscosity caprolactam monomer as an initial raw material, utilizes an anionic polymerization mechanism of the caprolactam monomer under the action of an initiator and a catalyst, controls a partially polymerized monomer or polymer mixed solution to be in a melt state, adopts a high-voltage electrostatic field as a fiber traction driving force, realizes the spinning and lapping of polycaprolactam superfine fiber, and simultaneously carries out polymerization reaction, high-molecular crystallization and electrostatic field force drafting molding to form a polycaprolactam superfine fiber two-dimensional porous membrane which is randomly distributed in one step; the spinning temperature is near the polymerization temperature of polycaprolactam and is lower than the melting point of polycaprolactam (nylon 6), the cooling speed of spinning jet flow is not required to be controlled, the bonding between fibers is avoided, and a good two-dimensional porous film form is ensured; the method does not use non-monomer organic solvent, does not have yield and cost loss caused by solvent volatilization, does not contain active ingredients used as solvent, does not have the phenomenon that the active ingredients are solidified into fibers, completes polymerization and spinning lapping conversion which are close to 100 percent, realizes electrostatic spinning of conventional linear thermoplastic polymer, and obtains the nano-scale to micron-scale superfine fiber non-woven two-dimensional film; simple process, convenient operation, safety, environmental protection and high yield, and belongs to green manufacturing. The chemical composition of the fiber in the non-woven two-dimensional film obtained by the invention is polycaprolactam (nylon 6), the fiber is a solid columnar fiber with a smooth surface, the diameter is in the range of 100 nanometers to 10 micrometers, and the fiber is laid in a random distribution mode; the non-woven two-dimensional membrane has excellent mechanical and engineering properties of nylon 6, controllable fiber diameter and micropore size, and heat resistance superior to that of a conventional polyolefin porous membrane, and can be used in the fields of gas-liquid multiphase filtration, porous media and the like.
Drawings
FIG. 1 is a schematic perspective view of an electrospinning apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic perspective view of an electrospinning apparatus used in a second embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of a resulting nonwoven two-dimensional film of one embodiment of the present invention;
FIG. 4 is a scanning electron microscope image of a nonwoven two-dimensional film obtained in example two of the present invention;
FIG. 5 is a scanning electron microscope photograph of a nonwoven two-dimensional film obtained in example four of the present invention;
FIG. 6 is a graph of differential scanning calorimetry test results for a nonwoven two-dimensional film obtained in example four of the present invention;
FIG. 7 is a graph of pore size analysis of a nonwoven two-dimensional membrane obtained in example four of the present invention;
in the figure: 1-a propulsion pump; 2-a syringe; 3-a catheter; 4-a radiant heat source; 5-Y type three-way connection; 6-wire clamp; 7-a needle head; 8-an insulating base; 9-a receiving plate; 10-a box body; 11-positive electrode high temperature resistant lead; 12-negative electrode high temperature resistant lead; 13-a positive high voltage power supply; 14-negative high voltage power supply.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of a polyamide superfine fiber non-woven two-dimensional film, which comprises the following steps:
1) taking a caprolactam monomer, adding an initiator, and melting to obtain a raw material A, wherein the molar ratio of the initiator to the caprolactam monomer is 1-10: 99-90;
2) taking caprolactam monomer, adding a catalyst, and melting to obtain a raw material B, wherein the molar ratio of the catalyst to the caprolactam monomer is 1-10: 99-90;
3) mixing the raw material A obtained in the step 1) and the raw material B obtained in the step 2) at a temperature of 80-200 ℃ in a fluid mixing part of a device to obtain a mixture;
4) and (3) further inputting the mixture obtained in the step 3) into spinning equipment equipped with a high-voltage electrostatic field, spinning in the electrostatic field and stretching under the electric field and the air field to form superfine fibers, wherein the voltage of the electrostatic field is 5-40 KV, and collecting random lapping of the superfine fibers on a receiving device to obtain the two-dimensional porous membrane.
Preferably, the catalyst is any one of sodium hydride, potassium hydride and lithium hydride.
Further, the catalyst is suspended in mineral oil, and the content of the catalyst in the mineral oil is 20-80%.
Preferably, the initiator is any one of TDI, MDI, IPDI, HMDI, HDI and LDI.
Preferably, the caprolactam monomer is dried in a vacuum drying oven at 55-65 ℃ for 20-30 hours before use to remove the contained moisture.
Preferably, in the electrostatic spinning equipment, the needle head is connected with a positive high-voltage power supply, the voltage of the positive high-voltage power supply is 5-25 KV, the receiving device is connected with a negative high-voltage power supply, and the voltage of the negative high-voltage power supply is-5-15 KV.
Further, the horizontal distance between the needle head and the receiving device is 15-20 cm.
The invention relates to a polyamide superfine fiber non-woven two-dimensional film, which is prepared according to the preparation method of the polyamide superfine fiber non-woven two-dimensional film.
As a preferred embodiment, the non-woven two-dimensional film further comprises any one or more of a filler, an inert filler and a non-reactive functional component not participating in the above polymerization reaction, and the total addition amount of the filler, the inert filler and the non-reactive functional component not participating in the above polymerization reaction is not more than 10% of the total weight of the non-woven two-dimensional film.
As a preferred embodiment, the filler is any one or more of a plasticizer, an antioxidant, an anti-aging agent and a toughening agent, and the inert filler is any one or more of talcum powder and quartz sand.
Example one
Referring to fig. 1, the electrospinning device of the present invention includes a manifold 10, and the manifold 10 may be set to a temperature sufficient to ensure a spinning temperature; the box body 10 can be an oven directly, and the box body 10 realizes temperature regulation through self-heating; a needle 7 is arranged on one side of the box body 10, a receiving device is arranged on the other side of the box body 10, the receiving device is a receiving plate 9, and the bottom of the receiving plate 9 is fixed in the box body 10 through an insulating base 8; the needle 7 is connected with a positive high-voltage power supply 13 through a positive high-temperature-resistant lead 11, the receiving plate 9 is connected with a negative high-voltage power supply 14 through a negative high-temperature-resistant lead 12, and direct-current high-voltage current enough to cause electrostatic spinning is formed between the needle 7 and the receiving plate 9. In general, the needle 7 is respectively connected with a conduit 3 for conveying the raw material A and a conduit 3 for conveying the raw material B through a Y-shaped three-way joint 5, the other end of the conduit 3 is connected with a syringe 2, and the syringe 2 is arranged on the propulsion pump 1; a lead wire clamp 6 is arranged between the needle 7 and the Y-shaped three-way joint 5, and the lead wire clamp 6 is connected to one end of the positive high-temperature-resistant lead 11 and used for fixing the needle 7; in addition, a radiation heating source 4 is provided outside the casing 10 at one side of the guide tube 3, and the radiation heating source 4 performs radiation heating from both sides of the guide tube 3 at the same time, thereby controlling the temperature of the injector 2 and the local area of the guide tube 3.
The invention relates to a preparation method of a polyamide superfine fiber non-woven two-dimensional film, which comprises the following steps:
1) taking caprolactam monomer, adding an initiator, namely toluene-2, 4-diisocyanate (TDI), wherein the molar ratio of the initiator to the caprolactam monomer is 7:93, mixing, placing in a drying oven at 180 ℃, and standing for 20min to melt the caprolactam monomer into liquid state to obtain a raw material A;
2) taking caprolactam monomer, adding a catalyst, namely sodium hydride, wherein the molar ratio of the catalyst to the caprolactam monomer is 7:93, mixing, placing in a drying oven at 180 ℃, and standing for 20min to melt the caprolactam monomer into liquid state to obtain a raw material B;
3) pumping the raw material A obtained in the step 1) into one glass injector 2 which is preheated in an oven at 180 ℃ in advance, and pumping the raw material B obtained in the step 2) into a second glass injector 2 which is preheated in the oven at 180 ℃ in advance; then, two glass syringes 2 are rapidly fixed on a propulsion pump 1, and are injected into a box body 10 of electrostatic spinning equipment at 180 ℃ through a guide pipe 3 at the perfusion speed of 8mL/h, the outside of the box body 10 is subjected to radiation heating from two sides by adopting a radiation heating source 4, so that the temperature of the local areas of the syringes 2 and the guide pipe 3 is maintained at 150 ℃, a raw material A and a raw material B are converged by a Y-shaped three-way joint 5, ring-opening polymerization is carried out, a melt is sticky and is extruded by a needle 7, the inner diameter of the needle 7 is 1.4mm, and a positive high-voltage power supply 13 of 20KV is connected;
4) the receiving device is a receiving plate 9, the receiving plate 9 is an aluminum metal plate, a layer of aluminum foil paper is wrapped outside the receiving plate 9, a negative high-voltage power supply 14 of 10KV is connected, the receiving distance between the receiving plate 9 and the needle 7 is 17cm, and lapping of the polyamide superfine fibers is received in a static mode, so that a two-dimensional porous membrane is formed.
The two-dimensional porous membrane obtained in the embodiment is observed in a scanning electron microscope of model MVE0352891782 produced by the company femina of germany, and as can be seen from the attached figure 3, the two-dimensional porous membrane obtained in the embodiment is composed of solid columnar fibers with smooth surfaces, the actually measured fiber diameter is about 6.8 μm, and the diameter distribution is uniform.
Example two
Referring to fig. 2, the electrospinning device of the present invention employs a mixing syringe 2 based on the first embodiment, so that only one syringe 2 is mounted on the propeller 1, the syringe 2 is connected to a conduit 3, and the conduit 3 is directly connected to the needle 7.
The invention relates to a preparation method of a polyamide superfine fiber non-woven two-dimensional film, which comprises the following steps:
1) taking caprolactam monomer, adding an initiator, namely toluene-2, 4-diisocyanate (TDI), wherein the molar ratio of the initiator to the caprolactam monomer is 5:95, mixing, placing in a drying oven at 180 ℃, standing for 20min, and melting into a liquid state to obtain a caprolactam molecular chain growth active center to obtain a raw material A;
2) taking caprolactam monomer, adding a catalyst, namely sodium hydride, wherein the molar ratio of the catalyst to the caprolactam monomer is 5:95, mixing, placing in a drying oven at 180 ℃, standing for 20min, and melting into a liquid state to obtain caprolactam anion to obtain a raw material B;
3) mixing the raw material A obtained in the step 1) and the raw material B obtained in the step 2) in an oven at 180 ℃, enabling caprolactam anions to continuously attack a molecular chain growth active center to perform a ring opening reaction to realize chain growth, continuously increasing melt viscosity, reacting for 3min until the conversion rate reaches 60% to obtain a mixture, and pumping the mixture into a glass injector 2 which is preheated in the oven at 180 ℃;
4) rapidly fixing the glass syringe 2 obtained in the step 3) on a propulsion pump 1, injecting the glass syringe 2 into a box body 10 of electrostatic spinning equipment at 180 ℃ through a guide pipe 3 at a perfusion speed of 4mL/h, carrying out radiation heating from two sides by adopting a radiation heating source 4 outside the box body 10, keeping the temperature of the local area of the syringe 2 and the guide pipe 3 at 150 ℃, ensuring that the mixture enters the box body 10 in a melt state with proper viscosity and is extruded out through a needle 7, wherein the inner diameter of the needle 7 is 1.4mm, and the needle is connected with a positive voltage power supply 12 of 20 KV;
5) the receiving device is a receiving plate 9, the receiving plate 9 is an aluminum metal plate, a layer of aluminum foil paper is wrapped outside the receiving plate 9, a negative high-voltage power supply 14 of 10KV is connected, the receiving distance between the receiving plate 9 and the needle 7 is 17cm, and lapping of the polyamide superfine fibers is received in a static mode, so that a two-dimensional porous membrane is formed.
The two-dimensional porous membrane obtained in the example was observed in a scanning electron microscope (MVE 0352891782 model, manufactured by Feina Germany), and as can be seen from FIG. 4, the two-dimensional porous membrane obtained in the example is composed of solid columnar fibers with smooth surfaces, and exists in the form of a random arrangement fiber membrane, and the measured average diameter of the fibers is 1.54 μm, and the diameters are uniformly distributed.
The two-dimensional porous membrane obtained in this example was placed in a Differential Scanning Calorimeter (DSC) model STARe Default DB V16.00 manufactured by mettler toledo corporation for testing; the differential scanning calorimetry test result showed that the fiber in the two-dimensional porous film obtained in this example had a melting temperature of 203.1 ℃, a melt crystallization temperature of 156.7 ℃, and a crystallinity of about 17.67%. Therefore, the melting point of the fibers in the two-dimensional porous membrane obtained by the invention is close to the melting point range of the conventional nylon 6 product, and the heat resistance is superior to that of the conventional polyolefin two-dimensional porous membrane; this demonstrates that the present invention can achieve high conversion of caprolactam monomer by polymerization in a short time.
The two-dimensional porous membrane obtained in this example was placed in a PSM165 type pore size tester manufactured by elm nit technologies ltd to perform a pore size test, and the test result showed that the average pore size of the two-dimensional porous membrane obtained in this example was 34.49 μm. Therefore, the two-dimensional porous membrane obtained by the invention has controllable micropore size and can be used in the fields of gas-liquid multiphase filtration, porous media and the like.
EXAMPLE III
On the basis of the second embodiment, the preparation method of the polyamide ultrafine fiber non-woven two-dimensional film of the embodiment comprises the following steps:
1) taking caprolactam monomer, adding an initiator, namely toluene-2, 4-diisocyanate (TDI), wherein the molar ratio of the initiator to the caprolactam monomer is 4:96, mixing, placing in a drying oven at 180 ℃, standing for 20min, and melting into a liquid state to obtain a caprolactam molecular chain growth active center to obtain a raw material A;
2) taking caprolactam monomer, adding a catalyst, namely sodium hydride, wherein the molar ratio of the catalyst to the caprolactam monomer is 4:96, mixing, placing in a drying oven at 180 ℃, standing for 20min, and melting into a liquid state to obtain caprolactam anion to obtain a raw material B;
3) mixing the raw material A obtained in the step 1) and the raw material B obtained in the step 2) in an oven at 200 ℃, enabling caprolactam anions to continuously attack a molecular chain growth active center to perform a ring opening reaction to realize chain growth, continuously increasing melt viscosity, reacting for 30min, and enabling the conversion rate to reach 60% to obtain a mixture, and pumping the mixture into a glass injector 2 which is preheated in the oven at 180 ℃ in advance;
4) rapidly fixing the glass syringe 2 obtained in the step 3) on a propulsion pump 1, injecting the glass syringe 2 into a box body 10 of electrostatic spinning equipment at 180 ℃ through a guide pipe 3 at a perfusion speed of 4mL/h, heating the outside of the box body 10 by adopting a radiation heating source 4 and simultaneously irradiating the box body with strong light to maintain the temperature of local areas of the syringe 2 and the guide pipe 3 at 180 ℃, ensuring that the mixture enters the inside of the box body 10 in a melt state with proper viscosity and is extruded out through a needle 7, wherein the inner diameter of the needle 7 is 1.4mm, and the needle is connected with a positive high-voltage power supply 13 of 20 KV;
5) the receiving device is a receiving plate 9, the receiving plate 9 is an aluminum metal plate, a layer of aluminum foil paper is wrapped outside the receiving plate 9, a negative high-voltage power supply 14 of 20KV is connected, the receiving distance between the receiving plate 9 and the needle 7 is 17cm, and lapping of the polyamide superfine fibers is received in a static mode, so that a two-dimensional porous membrane is formed.
The two-dimensional porous membrane obtained in the example was observed by placing the two-dimensional porous membrane in a scanning electron microscope of model MVE0352891782, manufactured by femina corporation, germany, and the result shows that the two-dimensional porous membrane obtained in the example is composed of solid columnar fibers with smooth surfaces, exists in the form of a random arrangement fiber membrane, and has the measured average fiber diameter of about 2.77 μm and uniform diameter distribution.
The two-dimensional porous membrane obtained in this example was placed in a Differential Scanning Calorimeter (DSC) model STARe Default DB V16.00 manufactured by mettler-toledo corporation for testing, and the DSC test result showed that the melting temperature of the fiber in the two-dimensional porous membrane obtained in this example was 206.5 ℃ and the crystallinity was about 23.92%. The melt crystallization temperature of the product was 166.8 ℃. Therefore, the melting point of the fibers in the two-dimensional porous membrane obtained by the invention is close to the melting point range of the conventional nylon 6 product, and the heat resistance is superior to that of the conventional polyolefin two-dimensional porous membrane; this shows that the invention makes it possible to achieve high conversions of caprolactam monomer by polymerization in a short time.
The two-dimensional porous membrane obtained in this example was placed in a PSM165 type pore size tester manufactured by elm nit technologies ltd to perform a pore size test, and the test result showed that the average pore size of the two-dimensional porous membrane obtained in this example was 50.74 μm. Therefore, the two-dimensional porous membrane obtained by the invention has controllable micropore size and can be used in the fields of gas-liquid multiphase filtration, porous media and the like.
Example four
On the basis of the second embodiment, the preparation method of the polyamide ultrafine fiber non-woven two-dimensional film of the embodiment comprises the following steps:
1) taking caprolactam monomer, adding an initiator, namely toluene-2, 4-diisocyanate (TDI), wherein the molar ratio of the initiator to the caprolactam monomer is 3:97, mixing, placing in a drying oven at 180 ℃, standing for 20min, and melting into a liquid state to obtain a caprolactam molecular chain growth active center to obtain a raw material A;
2) taking caprolactam monomer, adding a catalyst, namely sodium hydride, wherein the molar ratio of the catalyst to the caprolactam monomer is 3:97, mixing, placing in a drying oven at 180 ℃, standing for 20min, and melting into a liquid state to obtain caprolactam anion to obtain a raw material B;
3) mixing the raw material A obtained in the step 1) and the raw material B obtained in the step 2) in an oven at 180 ℃, enabling caprolactam anions to continuously attack a molecular chain growth active center to perform a ring opening reaction to realize chain growth, continuously increasing melt viscosity, reacting for 90min, and enabling the conversion rate to reach 60% to obtain a mixture, and pumping the mixture into a glass injector 2 which is preheated in the oven at 180 ℃ in advance;
4) rapidly fixing the glass syringe 2 obtained in the step 3) on a propulsion pump 1, injecting the glass syringe 2 into a box body 10 of electrostatic spinning equipment at 180 ℃ through a guide pipe 3 at a perfusion speed of 4mL/h, carrying out radiation heating from two sides by adopting a radiation heating source 4 outside the box body 10, keeping the temperature of the local area of the syringe 2 and the guide pipe 3 at 150 ℃, ensuring that the mixture enters the box body 10 in a melt state with proper viscosity and is extruded out through a needle head 7, wherein the inner diameter of the needle head 7 is 1.4mm, and the needle head is connected with a positive high-voltage power supply 13 of 20 KV;
5) the receiving device is a receiving plate 9, the receiving plate 9 is an aluminum metal plate, a layer of aluminum foil paper is wrapped outside the receiving plate 9, a negative high-voltage power supply 14 of 10KV is connected, the receiving distance between the receiving plate 9 and the needle 7 is 17cm, and lapping of the polyamide superfine fibers is received in a static mode, so that a two-dimensional porous membrane is formed.
The two-dimensional porous membrane obtained in this example was observed with a scanning electron microscope of model MVE0352891782, manufactured by femina, germany, and as can be seen from fig. 5, the two-dimensional porous membrane obtained in this example was composed of solid columnar fibers with smooth surfaces, and existed in the form of a random arrangement fiber membrane, and the measured average diameter of the fibers was about 0.61 μm, and the diameter distribution was uniform.
The two-dimensional porous film obtained in the example was placed in a Differential Scanning Calorimeter (DSC) model STARe Default DB V16.00 manufactured by mettler toledo corporation and tested, and as can be seen from fig. 6, the melting temperature of the fiber in the two-dimensional porous film obtained in the example was 212.8 ℃, the crystallinity was about 24.25%, and the melting and crystallization temperature of the product was 174.1 ℃.
The two-dimensional porous membrane obtained in this example was subjected to pore size analysis by a PSM165 type pore size tester manufactured by Elmenet technologies, Inc., and as can be seen from FIG. 7, the average pore size of the two-dimensional porous membrane obtained in this example was 6.87. mu.m.
Therefore, compared with the prior art, the invention has the beneficial effects that: the invention takes caprolactam monomer with low viscosity above the melting point as the initial raw material, utilizes the anionic polymerization mechanism of the caprolactam monomer under the action of an initiator and a catalyst to realize the simultaneous implementation of the mixing and polymerization reaction of low-viscosity polymerizable monomer, the conversion of the polymerization reaction into certain high-molecular-weight molten fluid, the fluid spinning and stretching, the high-molecular crystallization and the electrostatic field force drafting molding, and forms the polycaprolactam superfine fiber two-dimensional porous membrane with random arrangement by a one-step method; the spinning temperature is near the polymerization temperature of polycaprolactam and is far lower than the melting point of polycaprolactam, the cooling speed of spinning jet flow is not required to be controlled, the bonding between fibers is avoided, and the good two-dimensional porous film form is ensured; the preparation method does not use non-monomer organic solvent, does not have yield and cost loss caused by solvent volatilization, does not bring the consequences of solvent recovery and environmental pollution, completes polymerization and spinning lapping conversion which are close to 100 percent, realizes electrostatic spinning of the conventional linear thermoplastic polymer, and obtains the nano-scale to micron-scale superfine fiber non-woven two-dimensional film; the preparation process is simple, the operation is convenient, the safety and the environmental protection are realized, the yield is high, and the preparation method belongs to green manufacturing. The chemical composition of the fiber in the non-woven two-dimensional film obtained by the invention is polycaprolactam (nylon 6), the fiber is a solid columnar fiber with a smooth surface, the diameter is in the range of 100 nanometers to 10 micrometers, and the fiber is laid in a random distribution mode; the non-woven two-dimensional membrane has excellent mechanical and engineering properties of nylon 6, controllable fiber diameter and micropore size, and heat resistance superior to that of a conventional polyolefin porous membrane, and can be used in the fields of gas-liquid multiphase filtration, porous media and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a polyamide superfine fiber non-woven two-dimensional film material is characterized by comprising the following steps:
1) taking a caprolactam monomer, adding an initiator, and melting to obtain a raw material A, wherein the molar ratio of the initiator to the caprolactam monomer is 1-10: 99-90;
2) taking a caprolactam monomer, adding a catalyst, and melting to obtain a raw material B, wherein the molar ratio of the catalyst to the caprolactam monomer is 1-10: 99-90;
3) mixing the raw material A obtained in the step 1) and the raw material B obtained in the step 2) at a temperature of 80-200 ℃ in a fluid mixing part of a device to obtain a mixture;
4) and (3) further inputting the mixture obtained in the step 3) into spinning equipment equipped with a high-voltage electrostatic field, spinning in the electrostatic field and stretching under the electric field and the air field to form superfine fibers, wherein the voltage of the electrostatic field is 5-40 KV, and collecting random lapping of the superfine fibers on a receiving device to obtain the two-dimensional porous membrane.
2. The method of preparing a polyamide microfiber nonwoven two-dimensional film according to claim 1, wherein:
the catalyst is any one of sodium hydride, potassium hydride and lithium hydride.
3. The method of preparing a polyamide microfiber nonwoven two-dimensional film according to claim 2, wherein:
the catalyst is suspended in mineral oil, and the content of the catalyst in the mineral oil is 20-80%.
4. The method of preparing a polyamide microfiber nonwoven two-dimensional film according to claim 1, wherein:
the initiator is any one of TDI, MDI, IPDI, HMDI, HDI and LDI.
5. The method of preparing a polyamide microfiber nonwoven two-dimensional film according to claim 1, wherein:
the caprolactam monomer is dried in a vacuum drying oven at 55-65 ℃ for 20-30 hours before use to remove contained moisture.
6. The method for producing a polyamide ultrafine fiber nonwoven two-dimensional film according to any one of claims 1 to 5, characterized in that:
in the electrostatic spinning equipment, a needle head is connected with a positive high-voltage power supply, the voltage of the positive high-voltage power supply is 5-25 KV, a receiving device is connected with a negative high-voltage power supply, and the voltage of the negative high-voltage power supply is-5-15 KV.
7. The method of producing a polyamide microfiber nonwoven two-dimensional film according to claim 6, wherein:
the horizontal distance between the needle head and the receiving device is 15-20 cm.
8. A polyamide superfine fiber non-woven two-dimensional film is characterized in that:
the non-woven two-dimensional film is prepared by the preparation method of the polyamide superfine fiber non-woven two-dimensional film according to any one of claims 1 to 7.
9. The polyamide ultrafine fiber nonwoven two-dimensional film according to claim 8, characterized in that:
the non-woven two-dimensional film also comprises any one or more of a filling agent, an inert filling material and non-reactive functional components which do not participate in the polymerization reaction, and the total adding amount of the filling agent, the inert filling material and the non-reactive functional components which do not participate in the polymerization reaction is not more than 10 percent of the total weight of the non-woven two-dimensional film.
10. The polyamide ultrafine fiber nonwoven two-dimensional film according to claim 9, characterized in that:
the filler is any one or more of a plasticizer, an antioxidant, an anti-aging agent and a toughening agent, and the inert filler is any one or two of talcum powder and quartz sand.
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