CN117984635A - Antibacterial composite non-woven fabric - Google Patents

Antibacterial composite non-woven fabric Download PDF

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Publication number
CN117984635A
CN117984635A CN202410308231.2A CN202410308231A CN117984635A CN 117984635 A CN117984635 A CN 117984635A CN 202410308231 A CN202410308231 A CN 202410308231A CN 117984635 A CN117984635 A CN 117984635A
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stirring
flask
mixed solution
parts
reaction
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廖慧鹏
廖翱清
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Guangzhou Sanli Nonwoven Fabrics Co ltd
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Guangzhou Sanli Nonwoven Fabrics Co ltd
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Priority to CN202410308231.2A priority Critical patent/CN117984635A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/06—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D06M11/42—Oxides or hydroxides of copper, silver or gold
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses an antibacterial composite non-woven fabric which comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer, wherein one surface of the adsorption layer is in needling composite with the antibacterial layer, and the other surface of the adsorption layer is in mesh-shaped polyurethane hot melt adhesive with the breathable waterproof layer. The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 15-25 parts of flame retardant, 30-40 parts of mixed alcohol, 25-35 parts of polybutylene terephthalate and 1-3 parts of nano titanium dioxide. The synthesized flame retardant comprises a melamine structure, a phospholipid structure, an alkyl long chain and a benzophenone structure, has good dispersibility in modified polypropylene, and the obtained composite non-woven fabric has excellent flame retardance and ultraviolet resistance. The synthesized modified polypropylene comprises fluorocarbon chain segments, a sulfonamide structure, a quaternary ammonium salt structure, a maleic anhydride structure, an N-vinyl pyrrolidone structure and the like, so that the surface wettability of the adsorption layer is good, and the composite non-woven fabric is excellent in antibacterial property and heat resistance.

Description

Antibacterial composite non-woven fabric
Technical Field
The invention relates to the field of non-woven fabrics, in particular to an antibacterial composite non-woven fabric.
Background
Polypropylene fiber is a fiber product prepared from polypropylene as a raw material through melt spinning, and is the fastest growing variety in synthetic fibers in recent years, and can be divided into common filaments, composite fiber bulked yarns, short fibers, non-woven fabrics and the like according to a processing method. The non-woven fabric has the advantages of light weight, softness, ventilation, easy forming and the like, has rapid development, and is widely applied to the fields of disposable diapers, physiological supplies, sanitary products, clothing raw materials, bandages, packaging materials and the like. The polypropylene fiber has good physical and chemical properties, but because of the nonpolar structure, the molecular chain lacks hydrophilic groups, the product has poor hydrophilicity, and the application field is limited, so the polypropylene fiber is necessary to be hydrophilically modified to meet more use demands. The traditional method for enhancing the antibacterial property of the non-woven fabric is to add an antibacterial agent in a pretreatment or post-treatment mode, but the small molecular antibacterial agent has the risk of falling off after long-term use, so that the antibacterial property of the polymer is necessarily improved by a grafting and other modification methods, and the comprehensive performance of the non-woven fabric can meet the use requirement. Heretofore, it has been studied to prepare a maleic anhydride grafted polypropylene copolymer from a comonomer such as butyl methacrylate, to improve the hydrophilicity of polypropylene, and to develop a novel grafted monomer for simultaneously imparting antibacterial properties to nonwoven fabrics.
In addition, the polypropylene non-woven fabric is prepared by compounding polypropylene fiber monofilaments, so that the ignition point is low, the flame retardance is relatively poor, potential safety hazards exist in the use process of the polypropylene non-woven fabric, and the storage and the transportation of the non-woven fabric are also affected. The method for flame-retardant modification of the fabric by using the flame-retardant emulsion is one of important research methods at present, and the common flame-retardant monomers capable of preparing the flame-retardant emulsion of the fabric comprise phosphate esters, aluminum hydroxide, halogen flame retardants and the like, but the used flame-retardant monomers have the defects of insufficient photochemical stability and the like, so that the development of the flame-retardant monomers with excellent comprehensive performance is still an important research subject.
Disclosure of Invention
In order to solve the technical problems, the invention provides an antibacterial composite non-woven fabric.
The aim of the invention can be achieved by the following technical scheme:
an antibacterial composite non-woven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer, wherein one surface of the adsorption layer is subjected to needling to form the composite antibacterial layer, and the other surface of the adsorption layer is subjected to meshed polyurethane hot melt adhesive to form the breathable waterproof layer.
The antibacterial layer is prepared by padding cotton fibers in a silver ammonia solution of glucose, and drying and baking at 170 ℃; the silver ammonia solution of glucose is prepared by adding silver nitrate into deionized water, adding concentrated ammonia water and glucose solution, and mixing and stirring, wherein the dosage ratio of the silver nitrate to the deionized water to the concentrated ammonia water to the glucose solution is 1g:250g:2.5L:250g; the glucose solution is prepared by adding glucose into deionized water, stirring and mixing, wherein the dosage ratio of the glucose to the deionized water is 1g:250g.
The breathable waterproof layer is made of polyethylene fibers.
The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 15-25 parts of flame retardant, 30-40 parts of mixed alcohol, 25-35 parts of polybutylene terephthalate and 1-3 parts of nano titanium dioxide.
The volume ratio of the ethanol to the n-butanol with the volume fraction of 95 percent is 1: 1.
The flame retardant is prepared through the following steps:
step A1: adding phosphorus oxychloride into toluene, stirring and adding 2-hydroxy-4-n-octoxybenzophenone into the ice water bath at the temperature of 0 ℃, and stirring and reacting for 3-4 hours to obtain an intermediate a, wherein the dosage ratio of the phosphorus oxychloride, the toluene and the 2-hydroxy-4-n-octoxybenzophenone is 0.3mol:200mL:0.3mol;
in the reaction process, 2-hydroxy-4-n-octoxybenzophenone reacts with phosphorus oxychloride to generate a phosphoryl dichloride intermediate, wherein the structure of the intermediate a is shown as follows:
step A2: firstly, adding 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stirring and mixing to obtain a mixed solution 1, and preparing three parts of mixed solutions 1 for standby; adding the trichloronitrile and the 1, 4-dioxane into a flask, stirring for 5-10min, placing the flask in an ice-water bath at the temperature of 0 ℃, slowly dropwise adding a first part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 50 ℃, slowly dropwise adding a second part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 85 ℃, slowly dropwise adding a third part of mixed solution 1 into the flask under stirring, stirring for reaction for 11h, cooling to room temperature, adding deionized water, washing with deionized water, and drying in a drying box at the temperature of 60 ℃ for 12h to obtain an intermediate b, wherein the dosage ratio of the 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, the trichloronitrile and the 1, 4-dioxane is 0.30mol:0.30mol:180-210mL:0.10mol:300mL;
in the reaction process, 4-amino-4-methyl-pentan-1-ol and trichloronitrile react to remove hydrogen chloride to obtain an intermediate b, wherein the structure of the intermediate b is shown as follows:
Step A3: firstly, adding the intermediate a into acetonitrile, stirring and mixing to obtain a mixed solution 2 for later use; adding the intermediate b and triethylamine into a flask, placing the flask into an ice-water bath at the temperature of 0 ℃, slowly dropwise adding the mixed solution 2 into the flask under stirring, stirring for reacting for 1.5h after dropwise adding, then heating to the temperature of 40 ℃ for reacting for 11-12h, cooling to room temperature, filtering, washing the precipitate with deionized water and 1, 4-dioxane, and drying in a drying box at the temperature of 50-60 ℃ for 6-8h to obtain the flame retardant with hyperbranched macromolecules, wherein the dosage ratio of the intermediate a to acetonitrile to the intermediate b to the triethylamine is 0.03mol:150mL:0.02mol:0.06mol;
In the reaction process, the intermediate a and the intermediate b react to generate a phosphating product, which is a flame retardant with hyperbranched macromolecules, wherein the flame retardant comprises a melamine structure, a phosphating structure, an alkyl long chain and a benzophenone structure. The melamine structure and the phospholipid structure endow the flame retardant with the advantages of a phosphorus-nitrogen flame retardant system, and the combination of the melamine structure and the phospholipid structure can exert the synergistic flame retardant effect of condensed phases and gas phases; the nonpolar alkyl long chain has good compatibility with the polypropylene molecular chain, and the dispersibility of the flame retardant in polypropylene is enhanced; the benzophenone structure enables the flame retardant to have ultraviolet resistance.
The structure of the flame retardant is as follows:
The modified polypropylene is prepared by the following steps:
Step B1: adding 1- (3-aminopropyl) pyrrolidine into a round bottom flask with a magneton, and stirring in an ice-water bath at 0 ℃; adding perfluorooctyl sulfonyl fluoride into anhydrous toluene, stirring at room temperature for 10-15min to obtain a mixed solution a, slowly dripping the mixed solution a into the round-bottomed flask, stirring in an ice-water bath at 0 ℃ for reaction for 2h after dripping, heating to 45 ℃, stirring at constant temperature for reaction for 4-4.5h, steaming at 80 ℃ for 30-35min, suction filtering, recrystallizing in acetone, suction filtering, and finally drying in an oven at 40 ℃ for 4-6h to obtain the intermediate 1,1- (3-aminopropyl) pyrrolidine, perfluorooctyl sulfonyl fluoride and anhydrous toluene, wherein the dosage ratio of 0.01mol:0.01mol:55-65mL;
In the reaction process, 1- (3-aminopropyl) pyrrolidine reacts with perfluorooctyl sulfonyl fluoride to generate a sulfonamide compound, namely an intermediate 1, and the structure of the intermediate 1 is shown as follows:
Step B2: adding 2- (2-chloroethoxy) acetic acid into DMF, adding thionyl chloride under stirring, refluxing and stirring at 50 ℃ for 4-5h, filtering, extracting, and drying to obtain the intermediate 2,2- (2-chloroethoxy) acetic acid, wherein the dosage ratio of DMF to thionyl chloride is 0.1mol:100mL:0.2-0.3mol;
in the reaction process, 2- (2-chloroethoxy) acetic acid reacts with thionyl chloride to generate an intermediate 2, and the structure of the intermediate 2 is shown as follows:
Step B3: adding 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution b, adding the intermediate 2 into the dimethyl sulfoxide to obtain a mixed solution c, slowly dropwise adding the mixed solution c into the mixed solution b under the ice water bath at the temperature of 0 ℃, heating to the temperature of 40 ℃ after the dropwise adding is finished, reacting for 8-10 hours at constant temperature, distilling under reduced pressure to obtain an intermediate 3, wherein the dosage ratio of the intermediate 2, 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide is 0.1mol:0.1mol:0.01-0.015mol:100mL;
In the reaction process, 3- (hydroxymethyl) -4-methylfuran-2, 5-dione reacts with intermediate 2 to generate an esterification product, namely intermediate 3, and the structure of intermediate 3 is shown as follows:
Step B4: adding the intermediate 3 and the intermediate 1 into a flask, adding DMF, carrying out ultrasonic treatment for 30-40min, placing the flask into an oil bath at 90 ℃ for constant temperature stirring reaction for 24h, carrying out rotary evaporation, adding acetone into residues in the flask, adding petroleum ether, filtering, and drying to obtain an intermediate 4, wherein the dosage ratio of the intermediate 3 to the intermediate 1 to the DMF is 0.1mol:0.125-0.130mol:170-180mL;
in the reaction process, the intermediate 3 reacts with the intermediate 1 to generate an amphiphilic compound, namely an intermediate 4, and the structure of the intermediate 4 is shown as follows:
Step B5: adding polypropylene powder, dicumyl peroxide, an antioxidant 1010, an intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer, mixing for 20-30min to obtain a mixture, adding the mixture into a double-screw extruder at 200 ℃ for grafting reaction, and granulating to obtain modified polypropylene, wherein the dosage ratio of the polypropylene powder to the dicumyl peroxide to the antioxidant 1010 to the intermediate 4 to the N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:0.6-1.2g;
In the reaction process, polypropylene, an intermediate 4 and N-vinyl pyrrolidone are subjected to melt blending and grafting to obtain modified polypropylene, wherein the modified polypropylene comprises fluorocarbon chain segments, a sulfonamide structure, a quaternary ammonium salt structure, a maleic anhydride structure, an N-vinyl pyrrolidone structure and the like. The fluorocarbon chain segment has strong hydrophobicity and strong compatibility with polypropylene, can be wound with the main chain of polypropylene, and enhances the toughness of modified polypropylene; the sulfonamide structure has broad-spectrum antibacterial effect, so that the modified polypropylene has stronger resistance to most bacteria; the quaternary ammonium salt structure is water-soluble and antibacterial, and endows the modified polypropylene with hydrophilicity and antibacterial property; the grafting reaction of the maleic anhydride structure on the polypropylene is promoted by the N-vinyl pyrrolidone, the grafting rate is improved, the polar groups introduced after the grafting is successful, so that the acting force among molecules is enhanced, the molecular chain of the modified polypropylene is effectively nucleated, the crystallization of the molecular chain of the modified polypropylene is promoted, the solvent resistance and the permeability resistance of the modified polypropylene are improved, and the maleic anhydride derivative and the N-vinyl pyrrolidone structural unit are distributed on the polypropylene chain, so that the random fracture of the molecular chain in the thermal degradation process plays a certain role in blocking, and the thermal stability of the modified polypropylene is improved.
The invention has the beneficial effects that: the antibacterial composite non-woven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer. The adsorption layer comprises raw materials of modified polypropylene, a flame retardant, mixed alcohol, polybutylene terephthalate and nano titanium dioxide. The synthesized flame retardant comprises a melamine structure, a phospholipid structure, an alkyl long chain and a benzophenone structure. The melamine structure and the phospholipid structure endow the flame retardant with the advantages of a phosphorus-nitrogen flame retardant system, and the combination of the melamine structure and the phospholipid structure can exert the synergistic flame retardant effect of condensed phases and gas phases, so that the composite non-woven fabric has excellent flame retardant property; the benzophenone structure ensures that the flame retardant has ultraviolet resistance, improves the yellowing resistance of the composite non-woven fabric, and is convenient for transportation and storage; the nonpolar alkyl long chain has good compatibility with the polypropylene molecular chain, and enhances the dispersibility of the flame retardant in the polypropylene, so that the composite non-woven fabric has stable flame retardance and yellowing resistance.
In addition, the synthesized modified polypropylene is grafted into polypropylene by melt blending maleic anhydride derivative and N-vinyl pyrrolidone. The modified polypropylene comprises fluorocarbon chain segments, a sulfonamide structure, a quaternary ammonium salt structure, a maleic anhydride structure, an N-vinyl pyrrolidone structure and the like. The fluorocarbon chain section has strong hydrophobicity and strong compatibility with polypropylene, can be wound with the main chain of polypropylene, enhances the toughness of modified polypropylene and improves the mechanical property of the composite non-woven fabric; the sulfonamide structure has broad-spectrum antibacterial effect, so that the modified polypropylene has stronger resistance to most bacteria, and the composite non-woven fabric has broad-spectrum antibacterial property; the quaternary ammonium salt structure is water-soluble and antibacterial, and endows the modified polypropylene with hydrophilicity and antibacterial property, so that the composite non-woven fabric has a good antibacterial effect on escherichia coli and staphylococcus aureus, and the surface wettability of the composite non-woven fabric adsorption layer is improved; the grafting reaction of the maleic anhydride structure on the polypropylene is promoted by the N-vinyl pyrrolidone, the grafting rate is improved, the polar groups introduced after the grafting is successful, so that the acting force among molecules is enhanced, the molecular chain crystallization of the modified polypropylene is promoted, the solvent resistance and the permeation resistance of the modified polypropylene are improved, the solvent resistance and the permeation resistance of the composite non-woven fabric are also improved, the maleic anhydride derivative and the N-vinyl pyrrolidone structural unit are distributed on the polypropylene chain, the random fracture of the molecular chain in the thermal degradation process is blocked to a certain extent, and the thermal stability of the modified polypropylene is improved, so that the heat resistance of the composite non-woven fabric is enhanced.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A flame retardant prepared by the steps of:
step A1: adding phosphorus oxychloride into toluene, stirring and adding 2-hydroxy-4-n-octoxybenzophenone in an ice water bath at 0 ℃, and stirring and reacting for 3 hours to obtain an intermediate a, wherein the dosage ratio of the phosphorus oxychloride, the toluene and the 2-hydroxy-4-n-octoxybenzophenone is 0.3mol:200mL:0.3mol;
Step A2: firstly, adding 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stirring and mixing to obtain a mixed solution 1, and preparing three parts of mixed solutions 1 for standby; adding the trichloronitrile and the 1, 4-dioxane into a flask, stirring for 5min, placing the flask in an ice-water bath at 0 ℃, slowly dropwise adding a first part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 50 ℃, slowly dropwise adding a second part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 85 ℃, slowly dropwise adding a third part of mixed solution 1 into the flask under stirring, stirring for reaction for 11h, cooling to room temperature, adding deionized water, washing with deionized water, and drying in a drying box at 60 ℃ for 12h to obtain an intermediate b, wherein the dosage ratio of the 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, the trichloronitrile and the 1, 4-dioxane is 0.30mol:0.30mol:180mL:0.10mol:300mL;
step A3: firstly, adding the intermediate a into acetonitrile, stirring and mixing to obtain a mixed solution 2 for later use; adding the intermediate b and triethylamine into a flask, placing the flask into an ice-water bath at the temperature of 0 ℃, slowly dropwise adding the mixed solution 2 into the flask under stirring, stirring for reacting for 1.5 hours after dropwise adding, then heating to the temperature of 40 ℃ for reacting for 11 hours, cooling to room temperature, filtering, washing the precipitate with deionized water and 1, 4-dioxane, and drying in a drying box at the temperature of 50 ℃ for 6 hours to obtain the flame retardant with hyperbranched macromolecules, wherein the dosage ratio of the intermediate a, acetonitrile, the intermediate b and the triethylamine is 0.03mol:150mL:0.02mol:0.06mol.
Example 2
A flame retardant prepared by the steps of:
step A1: adding phosphorus oxychloride into toluene, stirring and adding 2-hydroxy-4-n-octoxybenzophenone into the toluene in an ice water bath at 0 ℃, and stirring and reacting for 3.5 hours to obtain an intermediate a, wherein the dosage ratio of the phosphorus oxychloride, the toluene and the 2-hydroxy-4-n-octoxybenzophenone is 0.3mol:200mL:0.3mol;
Step A2: firstly, adding 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stirring and mixing to obtain a mixed solution 1, and preparing three parts of mixed solutions 1 for standby; adding the trichloronitrile and the 1, 4-dioxane into a flask, stirring for 8min, placing the flask in an ice-water bath at 0 ℃, slowly dropwise adding a first part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 50 ℃, slowly dropwise adding a second part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 85 ℃, slowly dropwise adding a third part of mixed solution 1 into the flask under stirring, stirring for reaction for 11h, cooling to room temperature, adding deionized water, washing with deionized water, and drying in a drying box at 60 ℃ for 12h to obtain an intermediate b, wherein the dosage ratio of the 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, the trichloronitrile and the 1, 4-dioxane is 0.30mol:0.30mol:195mL:0.10mol:300mL;
Step A3: firstly, adding the intermediate a into acetonitrile, stirring and mixing to obtain a mixed solution 2 for later use; adding the intermediate b and triethylamine into a flask, placing the flask into an ice-water bath at 0 ℃, slowly dropwise adding the mixed solution 2 into the flask under stirring, stirring for reaction for 1.5h after dropwise adding, heating to 40 ℃ for 11h, cooling to room temperature, filtering, washing the precipitate with deionized water and 1, 4-dioxane, and drying in a drying box at 55 ℃ for 7h to obtain the flame retardant with hyperbranched macromolecules, wherein the dosage ratio of the intermediate a to acetonitrile to the intermediate b to the triethylamine is 0.03mol:150mL:0.02mol:0.06mol.
Example 3
A flame retardant prepared by the steps of:
Step A1: adding phosphorus oxychloride into toluene, stirring and adding 2-hydroxy-4-n-octoxybenzophenone into the toluene in an ice water bath at the temperature of 0 ℃, stirring and reacting for 4 hours to obtain an intermediate a, wherein the dosage ratio of the phosphorus oxychloride, the toluene and the 2-hydroxy-4-n-octoxybenzophenone is 0.3mol:200mL:0.3mol;
Step A2: firstly, adding 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stirring and mixing to obtain a mixed solution 1, and preparing three parts of mixed solutions 1 for standby; adding the trichloronitrile and the 1, 4-dioxane into a flask, stirring for 10min, placing the flask in an ice-water bath at 0 ℃, slowly dropwise adding a first part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 50 ℃, slowly dropwise adding a second part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 85 ℃, slowly dropwise adding a third part of mixed solution 1 into the flask under stirring, stirring for reaction for 11h, cooling to room temperature, adding deionized water, washing with deionized water, and drying in a drying box at 60 ℃ for 12h to obtain an intermediate b, wherein the dosage ratio of the 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, the trichloronitrile and the 1, 4-dioxane is 0.30mol:0.30mol:210mL:0.10mol:300mL;
step A3: firstly, adding the intermediate a into acetonitrile, stirring and mixing to obtain a mixed solution 2 for later use; adding the intermediate b and triethylamine into a flask, placing the flask into an ice-water bath at the temperature of 0 ℃, slowly dropwise adding the mixed solution 2 into the flask under stirring, stirring for reacting for 1.5 hours after dropwise adding, then heating to the temperature of 40 ℃ for reacting for 12 hours, cooling to room temperature, filtering, washing the precipitate with deionized water and 1, 4-dioxane, and drying in a drying box at the temperature of 60 ℃ for 8 hours to obtain the flame retardant with hyperbranched macromolecules, wherein the dosage ratio of the intermediate a, acetonitrile, the intermediate b and the triethylamine is 0.03mol:150mL:0.02mol:0.06mol.
Example 4
A modified polypropylene prepared by the steps of:
Step B1: adding 1- (3-aminopropyl) pyrrolidine into a round bottom flask with a magneton, and stirring in an ice-water bath at 0 ℃; adding perfluorooctyl sulfonyl fluoride into anhydrous toluene, stirring at room temperature for 10min to obtain a mixed solution a, slowly dripping the mixed solution a into the round-bottomed flask, stirring in an ice-water bath at 0 ℃ for reaction for 2h after dripping, heating to 45 ℃, stirring at constant temperature for reaction for 4h, rotary steaming at 80 ℃ for 30min, suction filtering, recrystallizing in acetone, suction filtering, and finally drying in an oven at 40 ℃ for 4h to obtain the intermediate 1,1- (3-aminopropyl) pyrrolidine, perfluorooctyl sulfonyl fluoride and anhydrous toluene, wherein the dosage ratio of the intermediate 1,1- (3-aminopropyl) pyrrolidine to the perfluorooctyl sulfonyl fluoride is 0.01mol:0.01mol:55mL;
Step B2: adding 2- (2-chloroethoxy) acetic acid into DMF, adding thionyl chloride under stirring, refluxing and stirring at 50 ℃ for reaction for 4 hours, filtering, extracting, and drying to obtain the intermediate 2,2- (2-chloroethoxy) acetic acid, wherein the dosage ratio of DMF to thionyl chloride is 0.1mol:100mL:0.2mol;
Step B3: adding 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution b, adding the intermediate 2 into the dimethyl sulfoxide to obtain a mixed solution c, slowly dropwise adding the mixed solution c into the mixed solution b under the ice water bath at the temperature of 0 ℃, heating to the temperature of 40 ℃ after the dropwise adding is finished, reacting for 8 hours at constant temperature, distilling under reduced pressure to obtain an intermediate 3, wherein the dosage ratio of the intermediate 2, 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide is 0.1mol:0.1mol:0.01mol:100mL;
Step B4: adding the intermediate 3 and the intermediate 1 into a flask, adding DMF, carrying out ultrasonic treatment for 30min, then placing the flask into an oil bath at 90 ℃ for constant temperature stirring reaction for 24h, carrying out rotary evaporation, adding acetone into residues in the flask, adding petroleum ether, filtering, and drying to obtain an intermediate 4, wherein the dosage ratio of the intermediate 3 to the intermediate 1 to the DMF is as follows: 0.1mol:0.125mol:170mL;
step B5: adding polypropylene powder, dicumyl peroxide, an antioxidant 1010, an intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer, mixing for 20min to obtain a mixture, adding the mixture into a double-screw extruder at 200 ℃ for grafting reaction, and granulating to obtain modified polypropylene, wherein the dosage ratio of the polypropylene powder to the dicumyl peroxide to the antioxidant 1010 to the intermediate 4 to the N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:0.6g.
Example 5
A modified polypropylene prepared by the steps of:
Step B1: adding 1- (3-aminopropyl) pyrrolidine into a round bottom flask with a magneton, and stirring in an ice-water bath at 0 ℃; adding perfluorooctyl sulfonyl fluoride into anhydrous toluene, stirring at room temperature for 12min to obtain a mixed solution a, slowly dripping the mixed solution a into the round-bottomed flask, stirring in an ice-water bath at 0 ℃ for reaction for 2h after dripping, heating to 45 ℃, stirring at constant temperature for reaction for 4.2h, steaming at 80 ℃ for 32min, suction filtering, recrystallizing in acetone, suction filtering, and finally drying in an oven at 40 ℃ for 5 to obtain the intermediate 1,1- (3-aminopropyl) pyrrolidine, perfluorooctyl sulfonyl fluoride and anhydrous toluene, wherein the dosage ratio of the intermediate 1,1- (3-aminopropyl) pyrrolidine to the perfluorooctyl sulfonyl fluoride is 0.01mol:0.01mol:60mL;
Step B2: adding 2- (2-chloroethoxy) acetic acid into DMF, adding thionyl chloride under stirring, refluxing and stirring at 50 ℃ for 4.5 hours, filtering, extracting, and drying to obtain an intermediate 2,2- (2-chloroethoxy) acetic acid, wherein the dosage ratio of DMF to thionyl chloride is 0.1mol:100mL:0.25mol;
Step B3: adding 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution b, adding the intermediate 2 into the dimethyl sulfoxide to obtain a mixed solution c, slowly dropwise adding the mixed solution c into the mixed solution b under the ice water bath at the temperature of 0 ℃, heating to the temperature of 40 ℃ after the dropwise adding is finished, reacting for 9 hours at constant temperature, distilling under reduced pressure to obtain an intermediate 3, wherein the dosage ratio of the intermediate 2,3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide is 0.1mol:0.1mol:0.012mol:100mL;
Step B4: adding the intermediate 3 and the intermediate 1 into a flask, adding DMF, carrying out ultrasonic treatment for 35min, then placing the flask into an oil bath at 90 ℃ for constant temperature stirring reaction for 24h, carrying out rotary evaporation, adding acetone into residues in the flask, adding petroleum ether, filtering, and drying to obtain an intermediate 4, wherein the dosage ratio of the intermediate 3 to the intermediate 1 to the DMF is 0.1mol:0.127mol:175mL;
Step B5: adding polypropylene powder, dicumyl peroxide, an antioxidant 1010, an intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer, mixing for 25min to obtain a mixture, adding the mixture into a double-screw extruder with the temperature of 200 ℃ for grafting reaction, and granulating to obtain modified polypropylene, wherein the dosage ratio of the polypropylene powder to the dicumyl peroxide to the antioxidant 1010 to the intermediate 4 to the N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:0.9g.
Example 6
A modified polypropylene prepared by the steps of:
Step B1: adding 1- (3-aminopropyl) pyrrolidine into a round bottom flask with a magneton, and stirring in an ice-water bath at 0 ℃; adding perfluorooctyl sulfonyl fluoride into anhydrous toluene, stirring at room temperature for 15min to obtain a mixed solution a, slowly dripping the mixed solution a into the round-bottomed flask, stirring in an ice-water bath at 0 ℃ for reaction for 2h after dripping, heating to 45 ℃, stirring at constant temperature for reaction for 4.5h, steaming at 80 ℃ for 35min, suction filtering, recrystallizing in acetone, suction filtering, and finally drying in an oven at 40 ℃ for 6h to obtain the intermediate 1,1- (3-aminopropyl) pyrrolidine, the perfluorooctyl sulfonyl fluoride and the anhydrous toluene, wherein the dosage ratio of the intermediate 1,1- (3-aminopropyl) pyrrolidine to the perfluorooctyl sulfonyl fluoride is 0.01mol:0.01mol:65mL;
Step B2: adding 2- (2-chloroethoxy) acetic acid into DMF, adding thionyl chloride under stirring, refluxing and stirring at 50 ℃ for reaction for 5 hours, filtering, extracting, and drying to obtain the intermediate 2,2- (2-chloroethoxy) acetic acid, wherein the dosage ratio of DMF to thionyl chloride is 0.1mol:100mL:0.3mol;
Step B3: adding 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution b, adding the intermediate 2 into the dimethyl sulfoxide to obtain a mixed solution c, slowly dropwise adding the mixed solution c into the mixed solution b under the ice water bath at the temperature of 0 ℃, heating to the temperature of 40 ℃ after the dropwise adding is finished, reacting for 10 hours at constant temperature, distilling under reduced pressure to obtain the intermediate 3, wherein the dosage ratio of the intermediate 2, 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide is 0.1mol:0.1mol:0.015mol:100mL;
Step B4: adding the intermediate 3 and the intermediate 1 into a flask, adding DMF, carrying out ultrasonic treatment for 40min, then placing the flask into an oil bath at 90 ℃ for constant temperature stirring reaction for 24h, carrying out rotary evaporation, adding acetone into residues in the flask, adding petroleum ether, filtering, and drying to obtain an intermediate 4, wherein the dosage ratio of the intermediate 3 to the intermediate 1 to the DMF is 0.1mol:0.130mol:180mL;
Step B5: adding polypropylene powder, dicumyl peroxide, an antioxidant 1010, an intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer, mixing for 30min to obtain a mixture, adding the mixture into a double-screw extruder with the temperature of 200 ℃ for grafting reaction, and granulating to obtain modified polypropylene, wherein the dosage ratio of the polypropylene powder to the dicumyl peroxide to the antioxidant 1010 to the intermediate 4 to the N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:1.2g.
Example 7
An antibacterial composite non-woven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer, wherein one surface of the adsorption layer is subjected to needling to form the composite antibacterial layer, and the other surface of the adsorption layer is subjected to meshed polyurethane hot melt adhesive to form the breathable waterproof layer.
The antibacterial layer is prepared by padding cotton fibers in a silver ammonia solution of glucose, and drying and baking at 170 ℃; the silver ammonia solution of glucose is prepared by adding silver nitrate into deionized water, adding concentrated ammonia water and glucose solution, and mixing and stirring, wherein the dosage ratio of the silver nitrate to the deionized water to the concentrated ammonia water to the glucose solution is 1g:250g:2.5L:250g; the glucose solution is prepared by adding glucose into deionized water, stirring and mixing, wherein the dosage ratio of the glucose to the deionized water is 1g:250g. The breathable waterproof layer is made of polyethylene fibers.
The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 15 parts of flame retardant, 30 parts of mixed alcohol, 25 parts of polybutylene terephthalate and 1 part of nano titanium dioxide; the volume ratio of the ethanol to the n-butanol with the volume fraction of 95 percent is 1:1, a mixture of two or more of the above-mentioned materials;
The adsorption layer is prepared by the following steps:
Step S1: drying the modified polypropylene and polybutylene terephthalate obtained in the example 4 for 4 hours at the temperature of 40 ℃, adding nano titanium dioxide, mixing by using a double screw extruder, and spinning; opening and mixing the spinning by using an opener to obtain opened spinning; carding the opened spinning, then lapping by using a lapping machine, finishing and forming, and then spinning by using a double-roller hot rolling machine, cooling and rolling to obtain the non-woven fabric. The roller shaft temperature of the double-roller hot rolling mill is 140 ℃;
Step S2: adding the flame retardant obtained in the example 1 into mixed alcohol, stirring for 10min to obtain flame-retardant emulsion, soaking the non-woven fabric in the flame-retardant emulsion for 20min, and then passing through a bench padder once; then soaking for 20min, passing through a bench padder for one time, and finally drying in an oven at 100 ℃ for 4h to obtain the adsorption layer.
The antibacterial composite non-woven fabric is prepared through the following steps:
And (3) attaching one side of the adsorption layer to the antibacterial layer, then compounding the adsorption layer by needling, and then attaching the other side of the adsorption layer to the breathable waterproof layer by using the reticular medical polyurethane hot melt adhesive to prepare the antibacterial composite non-woven fabric.
Example 8
An antibacterial composite non-woven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer, wherein one surface of the adsorption layer is subjected to needling to form the composite antibacterial layer, and the other surface of the adsorption layer is subjected to meshed polyurethane hot melt adhesive to form the breathable waterproof layer.
The antibacterial layer is prepared by padding cotton fibers in a silver ammonia solution of glucose, and drying and baking at 170 ℃; the silver ammonia solution of glucose is prepared by adding silver nitrate into deionized water, adding concentrated ammonia water and glucose solution, and mixing and stirring, wherein the dosage ratio of the silver nitrate to the deionized water to the concentrated ammonia water to the glucose solution is 1g:250g:2.5L:250g; the glucose solution is prepared by adding glucose into deionized water, stirring and mixing, wherein the dosage ratio of the glucose to the deionized water is 1g:250g. The breathable waterproof layer is made of polyethylene fibers.
The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 20 parts of flame retardant, 35 parts of mixed alcohol, 30 parts of polybutylene terephthalate and 2 parts of nano titanium dioxide; the volume ratio of the ethanol to the n-butanol with the volume fraction of 95 percent is 1:1, a mixture of two or more of the above-mentioned materials;
The adsorption layer is prepared by the following steps:
step S1: drying the modified polypropylene and polybutylene terephthalate obtained in the example 5 for 4 hours at the temperature of 40 ℃, adding nano titanium dioxide, mixing by using a double screw extruder, and spinning; opening and mixing the spinning by using an opener to obtain opened spinning; carding the opened spinning, then lapping by using a lapping machine, finishing and forming, and then spinning by using a double-roller hot rolling machine, cooling and rolling to obtain the non-woven fabric. The roller shaft temperature of the double-roller hot rolling mill is 145 ℃;
Step S2: adding the flame retardant obtained in the example 2 into mixed alcohol, stirring for 12min to obtain flame-retardant emulsion, soaking the non-woven fabric in the flame-retardant emulsion for 20min, and then passing through a bench padder once; then soaking for 20min, passing through a bench padder for one time, and finally drying in an oven at 100 ℃ for 4.5h to obtain the adsorption layer.
The antibacterial composite non-woven fabric is prepared through the following steps:
And (3) attaching one side of the adsorption layer to the antibacterial layer, then compounding the adsorption layer by needling, and then attaching the other side of the adsorption layer to the breathable waterproof layer by using the reticular medical polyurethane hot melt adhesive to prepare the antibacterial composite non-woven fabric.
Example 9
An antibacterial composite non-woven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer, wherein one surface of the adsorption layer is subjected to needling to form the composite antibacterial layer, and the other surface of the adsorption layer is subjected to meshed polyurethane hot melt adhesive to form the breathable waterproof layer.
The antibacterial layer is prepared by padding cotton fibers in a silver ammonia solution of glucose, and drying and baking at 170 ℃; the silver ammonia solution of glucose is prepared by adding silver nitrate into deionized water, adding concentrated ammonia water and glucose solution, and mixing and stirring, wherein the dosage ratio of the silver nitrate to the deionized water to the concentrated ammonia water to the glucose solution is 1g:250g:2.5L:250g; the glucose solution is prepared by adding glucose into deionized water, stirring and mixing, wherein the dosage ratio of the glucose to the deionized water is 1g:250g. The breathable waterproof layer is made of polyethylene fibers.
The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 25 parts of flame retardant, 40 parts of mixed alcohol, 35 parts of polybutylene terephthalate and 3 parts of nano titanium dioxide; the volume ratio of the ethanol to the n-butanol with the volume fraction of 95 percent is 1:1, a mixture of two or more of the above-mentioned materials;
The adsorption layer is prepared by the following steps:
Step S1: drying the modified polypropylene and polybutylene terephthalate obtained in the example 6 for 4 hours at the temperature of 40 ℃, adding nano titanium dioxide, mixing by using a double screw extruder, and spinning; opening and mixing the spinning by using an opener to obtain opened spinning; carding the opened spinning, then lapping by using a lapping machine, finishing and forming, and then spinning by using a double-roller hot rolling machine, cooling and rolling to obtain the non-woven fabric. The roll shaft temperature of the double-roll hot rolling mill is 150 ℃;
step S2: adding the flame retardant obtained in the example 3 into mixed alcohol, stirring for 15min to obtain flame-retardant emulsion, soaking the non-woven fabric in the flame-retardant emulsion for 20min, and then passing through a bench padder once; then soaking for 20min, passing through a bench padder for one time, and finally drying in an oven at 100 ℃ for 5h to obtain the adsorption layer.
The antibacterial composite non-woven fabric is prepared through the following steps:
and (3) attaching one side of the adsorption layer to the antibacterial layer, then compounding the adsorption layer by needling, and then adhering the other side of the adsorption layer to the breathable waterproof layer by using the meshed polyurethane hot melt adhesive to prepare the antibacterial composite non-woven fabric.
Comparative example 1
The comparative example was a commercially available composite nonwoven fabric.
Comparative example 2
In comparison with example 9, the flame retardant was replaced with melamine, and the other was identical to example 9, to prepare a composite nonwoven fabric.
Comparative example 2
In comparison with example 9, the modified polypropylene was changed to polypropylene, and the other was identical to example 9, to obtain a composite nonwoven fabric.
The properties of the obtained composite nonwoven fabrics were tested according to the relevant standards of GB/T21510-2008, FZ/T6000, GB/T5456-1997, GB/T18830 and the like, and the obtained results are shown in Table 1:
Table 1:
According to the data in table 1, it is clear from comparison of example 7, example 8 and example 9 with comparative example 1 that the antibacterial composite nonwoven fabric prepared by the invention has good inhibition effect on escherichia coli, staphylococcus aureus and salmonella enterica, and excellent mechanical property, flame retardant property and ultraviolet resistance compared with the commercially available composite nonwoven fabric. In example 9, compared with comparative example 2, it was found that the mechanical properties of the composite nonwoven fabric were decreased because the antibacterial groups such as quaternary ammonium salt and sulfonamide were not introduced, and the fluorocarbon segment, maleic anhydride and N-vinylpyrrolidone structure were not introduced by grafting, as compared with the composite nonwoven fabric prepared using the unmodified polypropylene. Compared with comparative example 3, the melamine as a flame retardant does not introduce a benzophenone structure, and the ultraviolet resistance of the obtained composite nonwoven fabric is reduced more.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (10)

1. An antibacterial composite nonwoven fabric, which is characterized in that: the anti-bacterial composite waterproof coating comprises an anti-bacterial layer, an adsorption layer and a breathable waterproof layer, wherein one surface of the adsorption layer is in needling composite with the anti-bacterial layer, and the other surface of the adsorption layer is in mesh-shaped polyurethane hot melt adhesive with the breathable waterproof layer; the antibacterial layer is prepared by padding cotton fibers in a silver ammonia solution of glucose, and drying and baking at 170 ℃; the silver ammonia solution of glucose is prepared by adding silver nitrate into deionized water, adding concentrated ammonia water and glucose solution, and mixing and stirring, wherein the dosage ratio of the silver nitrate to the deionized water to the concentrated ammonia water to the glucose solution is 1g:250g:2.5L:250g; the glucose solution is prepared by adding glucose into deionized water, stirring and mixing, wherein the dosage ratio of the glucose to the deionized water is 1g:250g; the breathable waterproof layer is made of polyethylene fibers;
The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 15-25 parts of flame retardant, 30-40 parts of mixed alcohol, 25-35 parts of polybutylene terephthalate and 1-3 parts of nano titanium dioxide; the volume ratio of the ethanol to the n-butanol with the volume fraction of 95 percent is 1: 1.
2. The antimicrobial composite nonwoven fabric according to claim 1, wherein: the flame retardant is prepared through the following steps:
Step A1: adding phosphorus oxychloride into toluene, stirring and adding 2-hydroxy-4-n-octoxybenzophenone into the ice water bath at the temperature of 0 ℃, and stirring and reacting for 3-4 hours to obtain an intermediate a;
Step A2: firstly, adding 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stirring and mixing to obtain a mixed solution 1, and preparing three parts of mixed solutions 1 for standby; adding trichloronitrile and 1, 4-dioxane into a flask, stirring for 5-10min, placing the flask into an ice-water bath at 0 ℃, slowly dripping a first part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 50 ℃, slowly dripping a second part of mixed solution 1 into the flask under stirring, stirring for reaction for 3h, heating to 85 ℃, slowly dripping a third part of mixed solution 1 into the flask under stirring, stirring for reaction for 11h, cooling to room temperature, adding deionized water, washing with deionized water, and drying in a drying box at 60 ℃ for 12h to obtain an intermediate b;
Step A3: firstly, adding the intermediate a into acetonitrile, stirring and mixing to obtain a mixed solution 2 for later use; adding the intermediate b and triethylamine into a flask, placing the flask into an ice-water bath at the temperature of 0 ℃, slowly dripping the mixed solution 2 into the flask under stirring, stirring for reaction for 1.5h after dripping, heating to the temperature of 40 ℃ for further reaction for 11-12h, cooling to room temperature, filtering, washing the precipitate with deionized water and 1, 4-dioxane, and drying in a drying box at the temperature of 50-60 ℃ for 6-8h to obtain the flame retardant with hyperbranched macromolecules.
3. The antimicrobial composite nonwoven fabric according to claim 1, wherein: the modified polypropylene is prepared by the following steps:
Step B1: adding 1- (3-aminopropyl) pyrrolidine into a round bottom flask with a magneton, and stirring in an ice-water bath at 0 ℃; adding perfluorooctyl sulfonyl fluoride into anhydrous toluene, stirring at room temperature for 10-15min to obtain a mixed solution a, slowly dripping the mixed solution a into the round-bottomed flask, stirring in an ice-water bath at 0 ℃ for reaction for 2h after dripping, heating to 45 ℃, stirring at constant temperature for reaction for 4-4.5h, steaming at 80 ℃ for 30-35min, suction filtering, recrystallizing in acetone, suction filtering, and finally drying in an oven at 40 ℃ for 4-6h to obtain an intermediate 1;
Step B2: adding 2- (2-chloroethoxy) acetic acid into DMF, adding thionyl chloride under stirring, refluxing and stirring at 50 ℃ for reaction for 4-5h, filtering, extracting and drying to obtain an intermediate 2;
Step B3: adding 3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution b, adding the intermediate 2 into the dimethyl sulfoxide to obtain a mixed solution c, slowly dropwise adding the mixed solution c into the mixed solution b under the ice water bath at the temperature of 0 ℃, heating to the temperature of 40 ℃ after the dropwise adding is finished, reacting for 8-10 hours at constant temperature, and distilling under reduced pressure to obtain an intermediate 3;
Step B4: adding the intermediate 3 and the intermediate 1 into a flask, adding DMF, carrying out ultrasonic treatment for 30-40min, placing the flask into an oil bath at 90 ℃ for constant temperature stirring reaction for 24h, carrying out rotary evaporation, adding acetone into residues in the flask, adding petroleum ether, filtering, and drying to obtain an intermediate 4;
Step B5: adding polypropylene powder, dicumyl peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer, mixing for 20-30min to obtain a mixture, adding the mixture into a double-screw extruder at 200 ℃ for grafting reaction, and granulating to obtain modified polypropylene.
4. An antimicrobial composite nonwoven according to claim 2, wherein: in the step A1, the ratio of phosphorus oxychloride, toluene and 2-hydroxy-4-n-octoxybenzophenone was 0.3mol:200mL:0.3mol.
5. An antimicrobial composite nonwoven according to claim 2, wherein: in step A2, the dosage ratio of 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, trichloronitrile and 1, 4-dioxane was 0.30mol:0.30mol:180-210mL:0.10mol:300mL.
6. An antimicrobial composite nonwoven according to claim 2, wherein: in step A3, the ratio of the amounts of intermediate a, acetonitrile, intermediate b and triethylamine was 0.03mol:150mL:0.02mol:0.06mol.
7. An antimicrobial composite nonwoven according to claim 3, wherein: in the step B1, the dosage ratio of 1- (3-aminopropyl) pyrrolidine, perfluorooctyl sulfonyl fluoride and anhydrous toluene was 0.01mol:0.01mol:55-65mL.
8. An antimicrobial composite nonwoven according to claim 3, wherein: in step B2, the ratio of 2- (2-chloroethoxy) acetic acid, DMF and thion was 0.1mol:100mL:0.2-0.3mol;
In step B3, the ratio of the amount of intermediate 2,3- (hydroxymethyl) -4-methylfuran-2, 5-dione, potassium carbonate and dimethyl sulfoxide was 0.1mol:0.1mol:0.01-0.015mol:100mL.
9. An antimicrobial composite nonwoven according to claim 3, wherein: in step B4, the ratio of the amounts of intermediate 3, intermediate 1 and DMF was 0.1mol:0.125-0.130mol:170-180mL.
10. An antimicrobial composite nonwoven according to claim 3, wherein: in the step B5, the dosage ratio of the polypropylene powder, the dicumyl peroxide, the antioxidant 1010, the intermediate 4 and the N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:0.6-1.2g.
CN202410308231.2A 2024-03-18 2024-03-18 Antibacterial composite non-woven fabric Pending CN117984635A (en)

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