CN114908479A - Production method of high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials - Google Patents
Production method of high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials Download PDFInfo
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- CN114908479A CN114908479A CN202210543187.4A CN202210543187A CN114908479A CN 114908479 A CN114908479 A CN 114908479A CN 202210543187 A CN202210543187 A CN 202210543187A CN 114908479 A CN114908479 A CN 114908479A
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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
- D04H13/00—Other non-woven fabrics
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- 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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
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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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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2509/00—Medical; Hygiene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention discloses a production method of a high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials, which specifically comprises the following steps: step S1: adding modified polyester into the modified cellulose solution, stirring, distilling to remove the solvent, adding the substrate into deionized water, continuously stirring, filtering again, and drying the substrate to obtain composite particles; step S2: uniformly mixing the composite particles, the porous filler, the fluorocarbon resin and the N, N-dimethylacetamide, carrying out electrostatic spinning, and collecting PBT melt-blown non-woven fabrics to obtain the double-layer melt-blown non-woven fabrics. The modified cellulose solution and the modified polyester are blended, and under an alkaline condition, amino groups on modified cellulose molecules react with epoxy groups on side chains of the modified polyester molecules to form a space structure with two molecular chains wrapped at intervals, so that the mechanical effect of the non-woven fabric is greatly improved.
Description
Technical Field
The invention relates to the technical field of preparation of medical supplies, in particular to a production method of a high-filtering low-resistance double-layer melt-blown non-woven fabric for a medical and health material.
Background
Nonwoven fabrics, also known as nonwovens, are composed of oriented or random fibers and are referred to as fabrics because of their appearance and certain properties. The non-woven fabric has no warp and weft, is very convenient to cut and sew, is light in weight and easy to shape, and is popular with hand fans. The non-woven fabric product is an environment-friendly product internationally recognized as the product for protecting the earth ecology, and has the advantages of rich color, brightness, fashion, environmental protection, wide application, beautiful appearance, various patterns and styles, light weight, environmental protection and recycling. The method is widely applied to the fields of chemical industry, automobile industry, household building materials, living decoration, medical treatment and health and the like.
The medical non-woven fabric has excellent performances in the aspects of elasticity and wear resistance, can recover automatically after deformation, and has a certain waterproof function and low production cost, so that the non-woven fabric has great market competitive advantages. Finally, the medical non-woven fabric has the performances of antibiosis and corrosion resistance, which is the most key characteristic of the medical non-woven fabric, other fabrics are difficult to replace, but the non-woven fabric has poor toughness and is easy to tear, and the use of the non-woven fabric is influenced.
Disclosure of Invention
The invention aims to provide a production method of a high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials, which solves the problem that the non-woven fabric is easy to tear and has a common filtering effect at the present stage.
The purpose of the invention can be realized by the following technical scheme:
a production method of a high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials comprises the following steps:
step S1: adding modified polyester into the modified cellulose solution, stirring for 2-3h at the rotation speed of 200-300r/min and the temperature of 25-30 ℃ under the alkaline condition, distilling to remove the solvent, adding the substrate into deionized water, continuously stirring for 3-5min, filtering again, and drying the substrate to obtain composite particles;
step S2: uniformly mixing the composite particles, the porous filler, the fluorocarbon resin and the N, N-dimethylacetamide, performing electrostatic spinning under the conditions that the propelling speed is 0.001-0.003mm/s, the voltage is 18-20kV and the receiving distance is 15-18cm, and collecting PBT melt-blown non-woven fabrics to obtain the double-layer melt-blown non-woven fabrics.
Further, the molar ratio of the amino group in the modified cellulose solution and the epoxy group in the modified polyester in step S1 is 1: 4.
Further, the mass ratio of the composite particles, the porous filler and the fluorocarbon resin in the step S2 is 5:0.02: 2.
Further, the modified cellulose solution is prepared by the following steps:
step A1: uniformly mixing 4,4' -dimethylbiphenyl and concentrated sulfuric acid, stirring and dripping a nitric acid solution at the room temperature at the rotation speed of 120-150r/min, reacting for 4-6h, cooling to the temperature of 0-3 ℃, filtering to remove filtrate to obtain an intermediate 1, dissolving the intermediate 1 in carbon tetrachloride, introducing chlorine gas under the illumination condition, and reacting for 1-1.5h to obtain an intermediate 2;
the reaction process is as follows:
step A2: dissolving the intermediate 2 in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions that the rotation speed is 120-minus-one (150 r/min) and the temperature is 100-minus-one (110 ℃), reacting for 30-40min, adjusting the pH value of the reaction solution to be alkaline to prepare an intermediate 3, mixing cellulose and N, N-dimethylacetamide, stirring for 2-3h under the conditions that the rotation speed is 300-minus-one (500 r/min) and the temperature is 130-minus-one (140 ℃), cooling to 90-100 ℃, adding lithium chloride, continuously stirring for 30-40min, cooling to 50-60 ℃, adding the intermediate 3, and continuously stirring for 7-9h to prepare the cellulose solution.
The reaction process is as follows:
further, the use amount ratio of the 4,4' -dimethylbiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step A1 is 0.01mol:20mL:6mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 60%, and the molar ratio of the intermediate 1 to the chlorine gas is 1:1.
Further, the dosage ratio of the intermediate 2, concentrated hydrochloric acid and tin powder in the step A2 is 3g:20mL:8g, the mass fraction of the concentrated hydrochloric acid is 36%, and the molar ratio of hydroxyl in the cellulose to the intermediate 3 is 1: 0.25.
The modified polyester is prepared by the following steps:
step B1: uniformly mixing 5-hydroxyisophthalic acid, methanol, concentrated sulfuric acid and hexane, carrying out reflux reaction for 5-7h at the temperature of 80-90 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, acetic anhydride and pyridine, continuously stirring for 2-4h at the temperature of 90-100 ℃ to obtain an intermediate 5, uniformly mixing sodium borohydride, lithium chloride and tetrahydrofuran, stirring and adding the intermediate 5 at the rotation speed of 150-200r/min at the temperature of 80-90 ℃, reacting for 3-5h, and then adjusting the pH value of a reaction solution to be acidic to obtain an intermediate 6;
the reaction process is as follows:
step B2: uniformly mixing the intermediate 6, terephthalic acid, ethylene glycol and antimony acetate, reacting for 4-6h under the conditions that the temperature is 220-250 ℃ and the pressure is 0.3-0.4MPa, heating to 280 ℃ and regulating the pressure to 50-60Pa, continuing to react for 1-2h to obtain polyester, dissolving the polyester in N, N-dimethylformamide, adding sodium carbonate and epoxy chloropropane, reacting for 2-4h under the conditions that the rotation speed is 200-300r/min and the temperature is 30-40 ℃, distilling to remove the solvent, adding deionized water, uniformly mixing, and filtering again to remove the filtrate to obtain the modified polyester.
Furthermore, in the step B1, the using amount ratio of the 5-hydroxyisophthalic acid, the methanol, the concentrated sulfuric acid and the hexane is 0.2mol:100mL:5mL:100mL, the mass fraction of the concentrated sulfuric acid is the same as that in the step A1, the using amount ratio of the intermediate 4, the acetic anhydride and the pyridine is 0.1mol:25mL:1mL, and the molar ratio of the sodium borohydride, the lithium chloride and the intermediate 5 is 2.5:2.5: 0.4.
Furthermore, the molar ratio of the intermediate 6, the terephthalic acid and the ethylene glycol in the step B2 is 0.05:1:1.5, the using amount of the antimony acetate is 0.05 percent of the mass of the reaction product, and the molar ratio of the hydroxyl group of the polyester to the epichlorohydrin is 1:1.
Further, the porous filler is prepared by the following steps:
mixing desiliconized high-alumina fly ash, alumina, kaolinite and carbon nano tubes, ball-milling uniformly, mixing uniformly with polyvinyl alcohol and ammonium bicarbonate, adding into a mold, performing pressure maintaining treatment for 2-3min under the condition that the pressure is 200-220MPa, and roasting for 2-3h under the condition that the temperature is 1200-1500 ℃ to prepare the porous filler.
Further, the mass ratio of the desiliconized high-alumina fly ash to the alumina to the kaolinite to the carbon nano tube is 6:2:1: 0.5.
The invention has the beneficial effects that: the invention discloses a medical health material, which is characterized in that modified cellulose liquid, modified polyester and porous filler are prepared in the process of preparing a high-filtration low-resistance double-layer melt-blown non-woven fabric, wherein the modified cellulose liquid is prepared by nitrating 4,4' -dimethylbiphenyl as a raw material to prepare an intermediate 1, the intermediate 1 is substituted by chlorine to prepare an intermediate 2, the intermediate 2 is reduced to reduce nitro groups into amino groups to prepare an intermediate 3, cellulose reacts with the intermediate 3 to react hydroxyl groups on the cellulose with chlorine atom sites on the intermediate 3 to generate cross-linking to prepare cellulose liquid, modified polyester 5-hydroxyisophthalic acid as a raw material is esterified with methanol to prepare an intermediate 4, the intermediate 4 reacts with acetic anhydride to prepare an intermediate 5, the intermediate 5 is reduced by sodium borohydride to prepare an intermediate 6, the intermediate 6, terephthalic acid and ethylene glycol are subjected to esterification polycondensation to prepare polyester, the polyester is reacted with epichlorohydrin, phenolic hydroxyl of a polyester side chain is reacted with chlorine atom sites on the epichlorohydrin to prepare modified polyester, modified cellulose liquid is blended with the modified polyester, amino on a modified cellulose molecule is reacted with epoxy groups on a modified polyester molecule side chain under an alkaline condition to form a space structure with two molecular chains wrapped at intervals, the structure greatly improves the mechanical effect of the non-woven fabric, the porous filler is prepared by ball-milling and roasting desiliconized high-alumina fly ash, alumina, kaolinite and carbon nano tubes, the porous filler contains a large number of pore channels which are communicated with each other and have through surfaces, the filtering effect of the non-woven fabric is greatly improved, the wear-resistant effect of the non-woven fabric is improved, the conductivity of the non-woven fabric is improved, and electrostatic adsorption of the non-woven fabric is avoided, so that the surface adsorbs dust and further the filtering effect is influenced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
A production method of a high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials comprises the following steps:
step S1: adding modified polyester into the modified cellulose solution, stirring for 2h at the rotation speed of 200r/min and the temperature of 25 ℃ under the alkaline condition, distilling to remove the solvent, adding the substrate into deionized water, continuously stirring for 3min, filtering again, and drying the substrate to obtain composite particles;
step S2: uniformly mixing the composite particles, the porous filler, the fluorocarbon resin and the N, N-dimethylacetamide, carrying out electrostatic spinning under the conditions that the advancing speed is 0.001mm/s, the voltage is 18kV and the receiving distance is 15cm, and collecting PBT melt-blown non-woven fabrics to prepare the double-layer melt-blown non-woven fabrics.
The molar ratio of the amino group in the modified cellulose solution and the epoxy group in the modified polyester described in step S1 was 1: 4.
The mass ratio of the composite particles, the porous filler and the fluorocarbon resin in the step S2 is 5:0.02: 2.
The modified cellulose solution is prepared by the following steps:
step A1: uniformly mixing 4,4' -dimethylbiphenyl and concentrated sulfuric acid, stirring and dropwise adding a nitric acid solution at the room temperature at the rotation speed of 120r/min, reacting for 4 hours, cooling to the temperature of 0 ℃, filtering to remove filtrate to obtain an intermediate 1, dissolving the intermediate 1 in carbon tetrachloride, introducing chlorine gas under the illumination condition, and reacting for 1 hour to obtain an intermediate 2;
step A2: dissolving the intermediate 2 in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions of a rotation speed of 120r/min and a temperature of 100 ℃, reacting for 30min, adjusting the pH value of a reaction solution to be alkaline to prepare an intermediate 3, mixing cellulose and N, N-dimethylacetamide, stirring for 2h under the conditions of a rotation speed of 300r/min and a temperature of 130 ℃, cooling to 90 ℃, adding lithium chloride, continuously stirring for 30min, cooling to 50 ℃, adding the intermediate 3, and continuously stirring for 7h to prepare a cellulose solution.
The using amount ratio of the 4,4' -dimethylbiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step A1 is 0.01mol:20mL:6mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 60%, and the molar ratio of the intermediate 1 to the chlorine gas is 1:1.
The dosage ratio of the intermediate 2, the concentrated hydrochloric acid and the tin powder in the step A2 is 3g to 20mL to 8g, the mass fraction of the concentrated hydrochloric acid is 36%, and the molar ratio of hydroxyl in the cellulose to the intermediate 3 is 1 to 0.25.
The modified polyester is prepared by the following steps:
step B1: uniformly mixing 5-hydroxyisophthalic acid, methanol, concentrated sulfuric acid and hexane, carrying out reflux reaction for 5 hours at the temperature of 80 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, acetic anhydride and pyridine, continuously stirring for 2 hours at the temperature of 90 ℃ to obtain an intermediate 5, uniformly mixing sodium borohydride, lithium chloride and tetrahydrofuran, stirring and adding the intermediate 5 at the rotation speed of 150r/min at the temperature of 80 ℃, reacting for 3 hours, and adjusting the pH value of a reaction solution to be acidic to obtain an intermediate 6;
step B2: uniformly mixing the intermediate 6, terephthalic acid, ethylene glycol and antimony acetate, reacting for 4 hours at 220 ℃ and 0.3MPa, heating to 260 ℃, adjusting the pressure to 50Pa, continuously reacting for 1 hour to obtain polyester, dissolving the polyester in N, N-dimethylformamide, adding sodium carbonate and epoxy chloropropane, reacting for 2 hours at the rotation speed of 200r/min and the temperature of 30 ℃, distilling to remove the solvent, adding deionized water, uniformly mixing, and filtering again to remove the filtrate to obtain the modified polyester.
The using amount ratio of the 5-hydroxyisophthalic acid, the methanol, the concentrated sulfuric acid and the hexane in the step B1 is 0.2mol:100mL:5mL:100mL, the mass fraction of the concentrated sulfuric acid is the same as that in the step A1, the using amount ratio of the intermediate 4, the acetic anhydride and the pyridine is 0.1mol:25mL:1mL, and the molar ratio of the sodium borohydride, the lithium chloride and the intermediate 5 is 2.5:2.5: 0.4.
The molar ratio of the intermediate 6, the terephthalic acid and the ethylene glycol in the step B2 is 0.05:1:1.5, the using amount of the antimony acetate is 0.05 percent of the mass of the reaction product, and the molar ratio of the hydroxyl group of the polyester to the epichlorohydrin is 1:1.
The porous filler is prepared by the following steps:
mixing the desiliconized high-alumina fly ash, alumina, kaolinite and carbon nano tubes, ball-milling uniformly, mixing uniformly with polyvinyl alcohol and ammonium bicarbonate, adding into a mold, performing pressure maintaining treatment for 2min under the condition of 200MPa, and roasting for 2h at the temperature of 1200 ℃ to prepare the porous filler.
The mass ratio of the desiliconized high-alumina fly ash to the alumina to the kaolinite to the carbon nano tube is 6:2:1: 0.5.
Example 2
A production method of a high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials comprises the following steps:
step S1: adding modified polyester into the modified cellulose solution, stirring for 2.5h under the conditions of the rotating speed of 200r/min, the temperature of 28 ℃ and alkalinity, distilling to remove the solvent, adding the substrate into deionized water, continuously stirring for 4min, filtering again, and drying the substrate to obtain composite particles;
step S2: the composite particles, the porous filler, the fluorocarbon resin and the N, N-dimethylacetamide are uniformly mixed, electrostatic spinning is carried out under the conditions that the propelling speed is 0.002mm/s, the voltage is 19kV and the receiving distance is 16cm, and the PBT melt-blown non-woven fabric is collected to prepare the double-layer melt-blown non-woven fabric.
The molar ratio of the amino group in the modified cellulose solution and the epoxy group in the modified polyester described in step S1 was 1: 4.
The mass ratio of the composite particles, the porous filler and the fluorocarbon resin in the step S2 is 5:0.02: 2.
The modified cellulose solution is prepared by the following steps:
step A1: uniformly mixing 4,4' -dimethylbiphenyl and concentrated sulfuric acid, stirring and dropwise adding a nitric acid solution at the room temperature at the rotation speed of 150r/min, reacting for 5 hours, cooling to the temperature of 2 ℃, filtering to remove filtrate to obtain an intermediate 1, dissolving the intermediate 1 in carbon tetrachloride, introducing chlorine gas under the illumination condition, and reacting for 1.3 hours to obtain an intermediate 2;
step A2: dissolving the intermediate 2 in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions of the rotation speed of 150r/min and the temperature of 105 ℃, reacting for 35min, adjusting the pH value of a reaction solution to be alkaline to prepare an intermediate 3, mixing cellulose and N, N-dimethylacetamide, stirring for 2.5h under the conditions of the rotation speed of 300r/min and the temperature of 135 ℃, cooling to 95 ℃, adding lithium chloride, continuously stirring for 35min, cooling to 55 ℃, adding the intermediate 3, and continuously stirring for 8h to prepare a cellulose solution.
The dosage ratio of the 4,4' -dimethylbiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step A1 is 0.01mol:20mL:6mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 60%, and the molar ratio of the intermediate 1 to the chlorine gas is 1:1.
The dosage ratio of the intermediate 2, the concentrated hydrochloric acid and the tin powder in the step A2 is 3g to 20mL to 8g, the mass fraction of the concentrated hydrochloric acid is 36%, and the molar ratio of hydroxyl in the cellulose to the intermediate 3 is 1 to 0.25.
The modified polyester is prepared by the following steps:
step B1: uniformly mixing 5-hydroxyisophthalic acid, methanol, concentrated sulfuric acid and hexane, carrying out reflux reaction for 6 hours at the temperature of 85 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, acetic anhydride and pyridine, continuously stirring for 3 hours at the temperature of 95 ℃ to obtain an intermediate 5, uniformly mixing sodium borohydride, lithium chloride and tetrahydrofuran, stirring and adding the intermediate 5 at the rotation speed of 180r/min at the temperature of 85 ℃, carrying out reaction for 4 hours, and adjusting the pH value of a reaction solution to be acidic to obtain an intermediate 6;
step B2: uniformly mixing the intermediate 6, terephthalic acid, ethylene glycol and antimony acetate, reacting for 5 hours at 230 ℃ and 0.3MPa, heating to 270 ℃, adjusting the pressure to 55Pa, continuously reacting for 1.5 hours to obtain polyester, dissolving the polyester in N, N-dimethylformamide, adding sodium carbonate and epoxy chloropropane, reacting for 3 hours at the rotation speed of 200r/min and the temperature of 35 ℃, distilling to remove the solvent, adding deionized water, uniformly mixing, and filtering again to remove the filtrate to obtain the modified polyester.
The using amount ratio of the 5-hydroxyisophthalic acid, the methanol, the concentrated sulfuric acid and the hexane in the step B1 is 0.2mol:100mL:5mL:100mL, the mass fraction of the concentrated sulfuric acid is the same as that in the step A1, the using amount ratio of the intermediate 4, the acetic anhydride and the pyridine is 0.1mol:25mL:1mL, and the molar ratio of the sodium borohydride, the lithium chloride and the intermediate 5 is 2.5:2.5: 0.4.
The molar ratio of the intermediate 6, the terephthalic acid and the ethylene glycol in the step B2 is 0.05:1:1.5, the using amount of the antimony acetate is 0.05% of the mass of the reactants, and the molar ratio of the hydroxyl group of the polyester to the epoxy chloropropane is 1:1.
The porous filler is prepared by the following steps:
mixing the desiliconized high-alumina fly ash, alumina, kaolinite and carbon nano tubes, ball-milling uniformly, mixing uniformly with polyvinyl alcohol and ammonium bicarbonate, adding into a mold, performing pressure maintaining treatment for 2.5min under the condition that the pressure is 210MPa, and roasting for 2.5h at the temperature of 1300 ℃ to obtain the porous filler.
The mass ratio of the desiliconized high-alumina fly ash to the alumina to the kaolinite to the carbon nano tube is 6:2:1: 0.5.
Example 3
A production method of a high-filtering low-resistance double-layer melt-blown non-woven fabric for medical and health materials specifically comprises the following steps:
step S1: adding modified polyester into the modified cellulose solution, stirring for 3h under the conditions of the rotating speed of 300r/min, the temperature of 30 ℃ and alkalinity, distilling to remove the solvent, adding the substrate into deionized water, continuously stirring for 5min, filtering again, and drying the substrate to obtain composite particles;
step S2: uniformly mixing the composite particles, the porous filler, the fluorocarbon resin and the N, N-dimethylacetamide, carrying out electrostatic spinning under the conditions that the propelling speed is 0.003mm/s, the voltage is 20kV and the receiving distance is 18cm, and collecting PBT melt-blown non-woven fabrics to prepare the double-layer melt-blown non-woven fabrics.
The molar ratio of the amino group in the modified cellulose solution and the epoxy group in the modified polyester described in step S1 was 1: 4.
The mass ratio of the composite particles, the porous filler and the fluorocarbon resin in the step S2 is 5:0.02: 2.
The modified cellulose solution is prepared by the following steps:
step A1: uniformly mixing 4,4' -dimethylbiphenyl and concentrated sulfuric acid, stirring and dropwise adding a nitric acid solution at the room temperature at the rotation speed of 150r/min, reacting for 6 hours, cooling to the temperature of 3 ℃, filtering to remove filtrate to obtain an intermediate 1, dissolving the intermediate 1 in carbon tetrachloride, introducing chlorine gas under the illumination condition, and reacting for 1.5 hours to obtain an intermediate 2;
step A2: dissolving the intermediate 2 in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions of the rotation speed of 150r/min and the temperature of 110 ℃, reacting for 40min, adjusting the pH value of the reaction solution to be alkaline to prepare an intermediate 3, mixing cellulose and N, N-dimethylacetamide, stirring for 3h under the conditions of the rotation speed of 500r/min and the temperature of 140 ℃, cooling to 100 ℃, adding lithium chloride, continuously stirring for 40min, cooling to 60 ℃, adding the intermediate 3, and continuously stirring for 9h to prepare cellulose solution.
The dosage ratio of the 4,4' -dimethylbiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step A1 is 0.01mol:20mL:6mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 60%, and the molar ratio of the intermediate 1 to the chlorine gas is 1:1.
The dosage ratio of the intermediate 2, the concentrated hydrochloric acid and the tin powder in the step A2 is 3g to 20mL to 8g, the mass fraction of the concentrated hydrochloric acid is 36%, and the molar ratio of hydroxyl in the cellulose to the intermediate 3 is 1 to 0.25.
The modified polyester is prepared by the following steps:
step B1: uniformly mixing 5-hydroxyisophthalic acid, methanol, concentrated sulfuric acid and hexane, carrying out reflux reaction for 7 hours at the temperature of 90 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, acetic anhydride and pyridine, continuously stirring for 4 hours at the temperature of 100 ℃ to obtain an intermediate 5, uniformly mixing sodium borohydride, lithium chloride and tetrahydrofuran, stirring and adding the intermediate 5 at the rotation speed of 200r/min at the temperature of 90 ℃, carrying out reaction for 5 hours, and adjusting the pH value of a reaction solution to be acidic to obtain an intermediate 6;
step B2: uniformly mixing the intermediate 6, terephthalic acid, ethylene glycol and antimony acetate, reacting for 6 hours at the temperature of 250 ℃ and the pressure of 0.4MPa, heating to 280 ℃, adjusting the pressure to 60Pa, continuously reacting for 2 hours to obtain polyester, dissolving the polyester in N, N-dimethylformamide, adding sodium carbonate and epoxy chloropropane, reacting for 4 hours at the rotation speed of 300r/min and the temperature of 40 ℃, distilling to remove the solvent, adding deionized water, uniformly mixing, and filtering again to remove the filtrate to obtain the modified polyester.
The using amount ratio of the 5-hydroxyisophthalic acid, the methanol, the concentrated sulfuric acid and the hexane in the step B1 is 0.2mol:100mL:5mL:100mL, the mass fraction of the concentrated sulfuric acid is the same as that in the step A1, the using amount ratio of the intermediate 4, the acetic anhydride and the pyridine is 0.1mol:25mL:1mL, and the molar ratio of the sodium borohydride, the lithium chloride and the intermediate 5 is 2.5:2.5: 0.4.
The molar ratio of the intermediate 6, the terephthalic acid and the ethylene glycol in the step B2 is 0.05:1:1.5, the using amount of the antimony acetate is 0.05 percent of the mass of the reaction product, and the molar ratio of the hydroxyl group of the polyester to the epichlorohydrin is 1:1.
The porous filler is prepared by the following steps:
mixing the desiliconized high-alumina fly ash, alumina, kaolinite and carbon nano tubes, ball-milling uniformly, mixing uniformly with polyvinyl alcohol and ammonium bicarbonate, adding into a mold, performing pressure maintaining treatment for 3min under the condition that the pressure is 220MPa, and roasting for 3h at the temperature of 1500 ℃ to obtain the porous filler.
The mass ratio of the desiliconized high-alumina fly ash to the alumina to the kaolinite to the carbon nano tube is 6:2:1: 0.5.
Comparative example 1
This comparative example is a PBT meltblown nonwoven.
Comparative example 2
Compared with the example 1, the non-woven fabric is prepared by directly performing electrostatic spinning on cellulose liquid and collecting the melt-blown non-woven fabric by using PBT (polybutylene terephthalate).
Comparative example 3
This comparative example is a nonwoven fabric disclosed in chinese patent CN 112853619A.
The nonwoven fabrics prepared in examples 1-3 and comparative examples 1-3 were measured for tensile strength with HD021NS electron single yarn dynamometer, and then with CLJ-03A laser dust particle counter, TSI-8108 large particle size aerosol generator, sampling flow rate of 2.83L/min, film thickness of 0.1mm, and filtration efficiency was measured, and the results are shown in the following table;
as can be seen from the above table, the tensile strength of the nonwoven fabrics prepared in examples 1 to 3 is 83.6 to 84.3MPa, and the filtration has a good filtration effect, which indicates that the nonwoven fabric has a good mechanical effect and a good filtration effect.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. The production method of the high-filtering low-resistance double-layer melt-blown non-woven fabric for the medical and health materials is characterized in that: the method specifically comprises the following steps:
step S1: adding modified polyester into the modified cellulose solution, stirring, distilling to remove the solvent, adding the substrate into deionized water, continuously stirring, filtering again, and drying the substrate to obtain composite particles;
step S2: and uniformly mixing the composite particles, the porous filler, the fluorocarbon resin and the N, N-dimethylacetamide, carrying out electrostatic spinning, and collecting PBT melt-blown non-woven fabrics to obtain the double-layer melt-blown non-woven fabrics.
2. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 1, characterized in that: the molar ratio of the amino group in the modified cellulose solution and the epoxy group in the modified polyester in the step S1 is 1:4, and the mass ratio of the composite particles, the porous filler and the fluorocarbon resin in the step S2 is 5:0.02: 2.
3. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 1, characterized in that: the modified cellulose solution is prepared by the following steps:
step A1: mixing 4,4' -dimethylbiphenyl and concentrated sulfuric acid for reaction, cooling, filtering and removing filtrate to obtain an intermediate 1, dissolving the intermediate 1 in carbon tetrachloride, introducing chlorine gas under the illumination condition, and reacting to obtain an intermediate 2;
step A2: dissolving the intermediate 2 in toluene, adding concentrated hydrochloric acid, stirring, adding tin powder, reacting, adjusting the pH value of the reaction solution to be alkaline to obtain an intermediate 3, mixing and stirring cellulose and N, N-dimethylacetamide, cooling, adding lithium chloride, continuously stirring, cooling again, adding the intermediate 3, and continuously stirring to obtain the cellulose solution.
4. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 3, characterized in that: the dosage ratio of the 4,4' -dimethylbiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step A1 is 0.01mol:20mL:6mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 60%, and the molar ratio of the intermediate 1 to the chlorine gas is 1:1.
5. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 3, characterized in that: the dosage ratio of the intermediate 2, the concentrated hydrochloric acid and the tin powder in the step A2 is 3g to 20mL to 8g, the mass fraction of the concentrated hydrochloric acid is 36%, and the molar ratio of hydroxyl in the cellulose to the intermediate 3 is 1 to 0.25.
6. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 1, characterized in that: the modified polyester is prepared by the following steps:
step B1: mixing 5-hydroxyisophthalic acid, methanol, concentrated sulfuric acid and hexane for reflux reaction to obtain an intermediate 4, mixing and stirring the intermediate 4, acetic anhydride and pyridine to obtain an intermediate 5, mixing and stirring sodium borohydride, lithium chloride and tetrahydrofuran, adding the intermediate 5 into the mixture, reacting, and adjusting the pH value of a reaction solution to obtain an intermediate 6;
step B2: mixing and reacting the intermediate 6, terephthalic acid, ethylene glycol and antimony acetate, heating, adjusting pressure, continuing to react to obtain polyester, dissolving the polyester in N, N-dimethylformamide, adding sodium carbonate and epoxy chloropropane, reacting, distilling to remove the solvent, adding deionized water, mixing uniformly, filtering again to remove the filtrate, and obtaining the modified polyester.
7. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 6, characterized in that: the using amount ratio of the 5-hydroxyisophthalic acid, the methanol, the concentrated sulfuric acid and the hexane in the step B1 is 0.2mol:100mL:5mL:100mL, the mass fraction of the concentrated sulfuric acid is the same as that in the step A1, the using amount ratio of the intermediate 4, the acetic anhydride and the pyridine is 0.1mol:25mL:1mL, and the molar ratio of the sodium borohydride, the lithium chloride and the intermediate 5 is 2.5:2.5: 0.4.
8. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 6, characterized in that: the molar ratio of the intermediate 6, the terephthalic acid and the ethylene glycol in the step B2 is 0.05:1:1.5, the using amount of the antimony acetate is 0.05 percent of the mass of the reaction product, and the molar ratio of the hydroxyl group of the polyester to the epichlorohydrin is 1:1.
9. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 1, characterized in that: the porous filler is prepared by the following steps:
mixing desiliconized high-alumina fly ash, alumina, kaolinite and carbon nano tubes, ball-milling uniformly, mixing uniformly with polyvinyl alcohol and ammonium bicarbonate, adding into a mold, performing pressure maintaining treatment for 2-3min under the condition that the pressure is 200-1500 MPa, and roasting for 2-3h under the condition that the temperature is 1200-1500 ℃ to obtain the porous filler.
10. The production method of the high-filtration low-resistance double-layer melt-blown nonwoven fabric for medical and health materials according to claim 9, characterized in that: the mass ratio of the desiliconized high-alumina fly ash to the alumina to the kaolinite to the carbon nano tube is 6:2:1: 0.5.
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