CN112553891B - Preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric - Google Patents

Abstract

A preparation method of a water-jet non-woven fabric for moisture-absorbing, breathable and antibacterial polyurethane synthetic leather comprises the steps of soaking 44.7g of pure cotton water-jet non-woven fabric in 70g of formic acid aqueous solution for 30 to 90min, taking out cotton textile fibers, putting the cotton textile fibers in 60g of acetic acid aqueous solution with the mass concentration of 15%, taking out after 30 to 150min, washing the cotton textile fibers for 3~5 times by 100ml of mixed solution of ethanol and water with the volume ratio of 70; dispersing 0.8g of sodium alginate, 0.7g of chitosan and 0.6g of emulsifier into 160g of distilled water, mixing and stirring for 50min at 60 ℃, adding 1.6g of modified cotton textile fiber and an antibacterial agent, soaking for 30-90min, taking out, then reacting for 0.5-3.5 h in 7g of soaking crosslinking agent and 80g of trifluoroacetic anhydride, drying for 15-40min at 100 ℃, washing for 3~5 times, and drying; and (3) uniformly scattering 15g of the obtained modified cocoanut bran product, 0.05g of carboxylated graphene sheet, 11.6g of polyurethane adhesive and 2.1g of substance on the surface of the moisture-absorbing and air-permeable spunlace woven material obtained in the step (3), folding the moisture-absorbing and air-permeable spunlace woven material in half, flattening, and placing the folded material in a 50 ℃ oven for heat preservation and reaction for 2-4 h to obtain the moisture-absorbing, air-permeable and antibacterial spunlace nonwoven fabric for polyurethane synthetic leather.

Description

Preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric

This application is a divisional application of 2018108507506.

technical field

The invention relates to a preparation method of a spunlace weaving material, especially a preparation method of a hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlace non-woven fabric.

Background technique

Non-woven fabrics have no warp and weft threads, are very convenient for cutting and sewing, and are light in weight and easy to shape, so they are deeply loved by handicraft lovers. Because it is a fabric that does not need spinning and weaving, it is just oriented or random arrangement of short textile fibers or filaments to form a web structure, and then reinforced by mechanical, thermal bonding or chemical methods.

It is not interwoven and braided by one yarn, but the fibers are directly bonded together through physical methods, so when you get the sticky scale in your clothes, you will find that, It is impossible to pull out a single thread. Nonwovens have broken through the traditional textile principles, and have the characteristics of short process flow, fast production rate, high output, low cost, wide application, and multiple sources of raw materials.

Spunbond fabrics and non-woven fabrics are subordinate. There are many production processes for the manufacture of non-woven fabrics, among which spunbond method is one of the non-woven fabric production processes (including spunbond method, melt blown method, hot rolling method, spunlace method, most of which are currently on the market Non-woven fabrics produced by spunbond method); non-woven fabrics include polyester, polypropylene, nylon, spandex, acrylic, etc. according to the composition; different compositions will have completely different styles of non-woven fabrics. The spunbond fabric usually refers to polyester spunbond and polypropylene spunbond; and the styles of these two fabrics are very similar, and can only be identified through high temperature testing.

Non-woven fabric is a kind of non-woven fabric, which directly uses polymer chips, short fibers or filaments to form fibers through airflow or machinery, and then undergoes hydroentanglement, needle punching, or hot rolling reinforcement, and finally finishes finishing Formed non-woven fabric. A new type of fiber product with soft, breathable and planar structure. The advantage is that it does not produce lint, is strong, durable, and silky soft. It is also a kind of reinforcing material, and it also has a cotton feel. Compared with cotton fabrics, non-woven fabrics Cloth bags are easy to form and inexpensive to make.

Its disadvantages are 1) poorer strength and durability compared to woven fabrics; 2) it cannot be washed like other fabrics; 3) the fibers are arranged in a certain direction, so it is easy to split from right angles, etc. Therefore, the improvement of the production method is mainly focused on the improvement of preventing splitting. (4) Poor water absorption; non-woven products are rich in color, bright and bright, fashionable and environmentally friendly, widely used, beautiful and generous, with various patterns and styles, and are light in weight, environmentally friendly and recyclable. They are internationally recognized as the best way to protect the earth's ecology Environmentally friendly products. Applicable to agricultural film, shoemaking, tanning, mattresses, quilts, decoration, chemical industry, printing, automobiles, building materials, furniture and other industries, as well as clothing interlining, medical disposable surgical gowns, masks, caps, bed sheets, hotels Disposable tablecloths, beauty, sauna and even today's fashionable gift bags, boutique bags, shopping bags, advertising bags and so on. Environmentally friendly products, versatile and economical. Because of its pearl-like appearance, it is also called pearl canvas.

Non-woven fabrics are made of chemical fibers and plant fibers on wet or dry paper machines under the condition of water or air as the suspension medium. Although they are cloth without weaving, they are called non-woven fabrics. Non-woven fabric is a new generation of environmentally friendly materials, which has the advantages of good strength, breathability and waterproof, environmental protection, flexibility, non-toxic and tasteless, and cheap price. It is a new generation of environmentally friendly materials, with the characteristics of water repellency, breathability, flexibility, non-combustibility, non-toxic and non-irritating, and rich colors. If the material is naturally decomposed outdoors, its longest lifespan is only 90 days, and it decomposes within 8 years when placed indoors. It is non-toxic and harmless when burned, so it does not pollute the environment, so environmental protection comes from this.

(1) Medical and sanitary non-woven fabrics: surgical gowns, protective clothing, disinfection wraps, masks, diapers, civilian rags, wiping cloths, wet face towels, magic towels, soft towel rolls, beauty products, sanitary napkins, sanitary care Pads, and disposable sanitary cloths, etc.

(2) Non-woven fabrics for home decoration: wall coverings, tablecloths, bed sheets, bedspreads, etc.

(3) Non-woven fabrics for clothing: lining, fusible interlining, flakes, shaped cotton, various synthetic leather base fabrics, etc.

(4) Non-woven fabrics for industrial use; base materials for roofing waterproof membranes and asphalt tiles, reinforcing materials, polishing materials, filter materials, insulating materials, cement packaging bags, geotextiles, covering cloths, etc.

(5) Agricultural non-woven fabrics: crop protection fabrics, seedling raising fabrics, irrigation fabrics, thermal insulation curtains, etc.

(6) Other non-woven fabrics: space cotton, thermal insulation and sound insulation materials, linoleum, cigarette filters, tea bags, shoe materials, etc.

Medical and health: surgical gowns, caps, covers, gypsum cotton wool, women's sanitary napkins, baby diapers, wet face towels, sanitary underwear, dust covers.

Agriculture: harvest cloth, greenhouse cloth.

Industry: floppy disk lining, speaker cloth, filter material, speaker sound insulation felt, sealing ring lining, cable cloth, fiberglass reinforced towel, industrial wipe, shockproof pad, insulation material, tape base lining, pipe base lining, ventilation pipe, Shapi cloth.

Packing: compound cement bag, luggage lining cloth, packaging base lining, wadding, storage bag, mobile jacquard luggage cloth.

Clothing and shoemaking: clothing lining, flakes, hard toe lining, heel lining, underwear, artificial deerskin, synthetic leather, warm shoe lining, cloth sole lining.

Automobile industry: waste spinning insulation thermal felt, anti-shock felt, canopy, seat cushion lining, carpet, car door lining, car filter element, molded seat cushion.

Household clothing: sofa inner cloth, carpet, wall covering, mirror cleaning cloth, tea bag, vacuum cleaner filter bag, shopping bag, printed bed sheet, entertainment cover, cushion, sleeping bag, dry cleaning cloth, scouring pad, curtain, tablecloth, Lampshade, and the back of the Mito mat is covered with film.

Civil engineering, construction: reinforcement, reinforcement, filtration, linoleum base fabric, drainage board, roof waterproofing material, railway, highway, berm, water slope, port sound insulation, sewer, heat protection, separation, drainage.

Other uses: launch vehicle, missile head heat-proof cone, tail nozzle throat lining, high-grade banknote printing paper, space shuttle heat-resistant tile, map cloth, calendar cloth, artificial cloth, oil painting cloth and so on.

Coconut peat refers to the fiber powder of coconut husk, which is a pure natural organic medium that falls off during the processing of coconut husk fiber, and is a by-product or waste of coconut after processing. Coconut peat has good water retention. It can fully maintain the nutrients and water needed for plant growth, reduce the loss of water and nutrients, and allow the roots of the plants to absorb more water and nutrients during the growth period. Second, coconut bran has good air permeability. It can effectively prevent the root system of plants from decaying and promote the healthy development of plant roots; it can also protect the soil and avoid soil muddying. The cost of coconut peat is lower.

201711233692.4 An antibacterial agent for non-woven fabrics, consisting of the following raw materials in parts by weight: 40-50 parts of ethanol, 10-14 parts of polyether siloxane, 4-6 parts of preservatives, 1-3 parts of formaldehyde, ammonium citrate 5-9 parts, titanium dioxide 8-12 parts, silicon dioxide 12-16 parts, zinc oxide 12-16 parts, magnesium oxide 2-4 parts, silver oxide 2-4 parts, water 60-70 parts. The beneficial effects of the present invention are as follows: (1) The source of raw materials is abundant, the manufacturing cost is low, the preparation is convenient, and the non-woven fabric can have the functions of sterilization, deodorization and anti-ultraviolet rays, and it is washable, non-toxic and harmless; (2) Environmental protection Strong resistance, good durability, can be widely used in textile fiber products.

Contents of the invention

The present invention relates to the preparation method of hygroscopic, breathable, antibacterial polyurethane synthetic leather spunlaced non-woven fabric, which will use the coconut bran modified product to improve the hygroscopicity of the material, 4-acetoxystyrene and tetraalkylammonium fluoride Improve its water absorption effect, trifluoroacetic anhydride improves the fixing effect of antibacterial agents, and maintains the long-lasting antibacterial effect, lithium diisopropylamide and 2-hydroxypropanetricarboxylic acid improve the antibacterial effect of antibacterial agents, and substance A improves the antibacterial effect of polyurethane adhesives The dispersibility of the polyurethane makes the polyurethane hygroscopic, breathable and antibacterial.

The preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric is characterized in that:

(1) Preparation of modified coconut peat products: add 44.5g of modified coconut peat that has been crushed to 1-2mm into 32g of diethylaluminum hypophosphite, 3.1g of diethylenetriaminepentaacetic acid, and then add 180ml of water , stirred and reacted at 95°C for 1~2h, then added 0.7g of potassium hydrogen tartrate, 2.6g of diethylenetriaminepentaacetic acid, reacted at 60°C for 2h, then added 0.5g of 4-acetoxystyrene and tetraalkyl fluoride Ammonium chloride 6.2g, react at 70°C for 1~3h, stand still for 0.6h, and dry at 105°C for 2h to obtain the modified coconut bran product.

(2) Preparation of modified cotton textile fibers: immerse 44.7g of pure cotton spunlace nonwoven fabric in 70g of 5% formic acid aqueous solution at 25~60°C for 30~90min, take out the cotton textile fibers and put them in the mass fraction 60g acetic acid aqueous solution with a concentration of 15%, take it out after 30~150min, then wash 3~5 times with 100ml of a mixed solution of ethanol and water with a volume ratio of 70:30, and dry;

(3) Preparation of hygroscopic and breathable spunlace woven materials: disperse 0.8g of sodium alginate, 0.7g of chitosan, and 0.6g of emulsifier into 160g of distilled water, mix and stir at 60°C for 50min, add step (2) to modify 1.6g of permanent cotton textile fiber and antibacterial agent, soaked for 30~90min, took out, then soaked in water of 7g of crosslinking agent and 80g of trifluoroacetic anhydride, reacted for 0.5~3.5h, dried at 100°C for 15~40min, washed with water for 3~5 times, just dry;

(4) Preparation of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric: 15g of modified coconut bran product obtained in step (1), 0.05g of carboxylated graphene sheet, 11.6g of polyurethane adhesive and substance A2.1g is evenly sprinkled on the surface of the hygroscopic and breathable spunlace woven material obtained in step (3), and the obtained hygroscopic and breathable spunlace woven material is folded in half, flattened, and placed in a 50°C oven for 2 to 4 hours. Acquired hygroscopic, breathable, antibacterial polyurethane synthetic leather spunlace non-woven fabric.

The emulsifier is any one of sodium stearoyl lactylate, Pingpingjia O, sodium carboxymethylcellulose, diacetyl tartaric acid monoglyceride DATEM;

The crosslinking agent is any one of 3,4-dihydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, trimethylhydroxyethylpropylenediamine, and hydroxyethylacrylamide;

Carboxylated graphene sheet: Graphene 0.012g sheet was added to concentrated sulfuric acid 400ml, 4-triphenylamine borate 0.3g and 3,4,5-trifluorophenylboronic acid 0.3g and mixed, the reaction temperature was 80°C, in Condensate and reflux in an ultrasonic cleaner with an ultrasonic power of 500W and an ultrasonic frequency of 100KHz for 2 hours, dilute with 450mL deionized water after ultrasonication, and then filter with a microporous membrane with a diameter of 0.2μm, and wash repeatedly with deionized water until neutral. Finally, bake at 80°C for 8 hours, and grind to a fine powder to obtain a carboxylated graphene sheet, and graphene is a graphene sheet produced by chemical vapor deposition;

Preparation of polyurethane adhesive: It is prepared from the invention patent 201510974180.8, a method for preparing a transparent matte water-based polyurethane emulsion and Example 1 of the transparent matte water-based polyurethane emulsion prepared by this method.

The preparation method of the described antibacterial agent is: 10g of 5-hydroxytryptophan, 3 ~ 4g of homatropine hydrobromide and 2 ~ 3g of 2-bromo-2-nitro-1,3-propanol are added to three ports In the flask, stir and react at 60°C for 1~2h, then add 1~3g of 1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid, stir and react at 70°C for 1~3h , then add 1~2g of 2,3-pyrazinedicarboxylic acid, 1~2g of aluminum sulfate, 15~30g of water, 2~3g of lithium diisopropylamide and 1.2g of 2-hydroxypropanetricarboxylic acid, at 65℃ Stirring and reacting for 2~3h, vacuum drying at 45°C for 1h, to obtain the antibacterial agent.

The preparation method of substance A is: transesterify 15g of methyl cyclohexyl propionate, 12g of hydroxyethyl acrylate and 0.5g of p-toluenesulfonic acid at 90-120°C for 1-2h, then add 2-hydroxyethylamine 1.3 g, 1.4g of acrylamide and 1.3g of 3-aminopropyltrihydroxysilane, 1~2h at 80~110℃, then add 1~2g of benzyl chloride (benzyl chloride) and 1.2~1.6g of trimethylolpropane , at 60-70°C for 1-2h, and dried at 40°C to obtain substance A.

The advantages of the present invention are:

(1) Coconut by-products or wastes have good water retention of coconut peat. This invention utilizes the good water retention of coconut peat to improve the hygroscopicity of materials by using coconut peat modified products. 4-Acetoxystyrene and four Alkyl ammonium fluoride improves its water absorption effect, trifluoroacetic anhydride improves the immobilization effect of antibacterial agents, and maintains a long-lasting antibacterial effect, lithium diisopropylamide and 2-hydroxypropanetricarboxylic acid improve the antibacterial effect of antibacterial agents, substance A Improve the dispersibility of the polyurethane adhesive, so that the polyurethane has moisture absorption, air permeability and antibacterial properties.

(2) Graphene was purchased from Chongqing Moxi Technology Co., Ltd., but the invention is not limited to the above manufacturers.

detailed description

Example 1

The preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric is characterized in that:

(1) Preparation of modified coconut peat products: add 44.5g of modified coconut peat that has been crushed to 1-2mm into 32g of diethylaluminum hypophosphite, 3.1g of diethylenetriaminepentaacetic acid, and then add 180ml of water , stirred and reacted at 95°C for 1h, then added 0.7g of potassium hydrogen tartrate, 2.6g of diethylenetriaminepentaacetic acid, reacted at 60°C for 2h, then added 0.5g of 4-acetoxystyrene and tetraalkylammonium fluoride 6.2g, react at 70°C for 1h, let stand for 0.6h, and dry at 105°C for 2h to obtain the modified coconut bran product.

(2) Preparation of modified cotton textile fibers: immerse 44.7g of pure cotton spunlaced nonwoven fabric in 70g of 5% formic acid aqueous solution by mass fraction, soak for 30min at 25°C, take out the cotton textile fibers, and put them in a concentration of 15% 60g of acetic acid aqueous solution, take it out after 30min, then wash 3 times with 100ml of ethanol and water mixed solution with a volume ratio of 70:30, and dry;

(3) Preparation of hygroscopic and breathable spunlace woven materials: disperse 0.8g of sodium alginate, 0.7g of chitosan, and 0.6g of sodium stearoyl lactylate into 160g of distilled water, mix and stir at 60°C for 50min, add step (2 ) modified cotton textile fiber and 1.6g of antibacterial agent, soaked for 30min, took out, then soaked in 3,4-dihydroxyphenylacetic acid 7g and trifluoroacetic anhydride 80g water, reacted for 0.5h, dried at 100°C for 15min, washed 3 times with water , just dry;

(4) Preparation of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric: 15g of modified coconut bran product obtained in step (1), 0.05g of carboxylated graphene sheet, 11.6g of polyurethane adhesive and substance A2.1g is evenly sprinkled on the surface of the hygroscopic and breathable spunlace woven material obtained in step (3), and the obtained hygroscopic and breathable spunlace woven material is folded in half, flattened, and placed in a 50°C oven to keep warm for 2 hours to obtain moisture absorption. , breathable, antibacterial polyurethane synthetic leather spunlace non-woven fabric.

Carboxylated graphene sheet: Graphene 0.012g sheet was added to concentrated sulfuric acid 400ml, 4-triphenylamine borate 0.3g and 3,4,5-trifluorophenylboronic acid 0.3g and mixed, the reaction temperature was 80°C, in Condensate and reflux in an ultrasonic cleaner with an ultrasonic power of 500W and an ultrasonic frequency of 100KHz for 2 hours, dilute with 450mL deionized water after ultrasonication, and then filter with a microporous membrane with a diameter of 0.2μm, and wash repeatedly with deionized water until neutral. Finally, bake at 80°C for 8 hours, and grind to a fine powder to obtain a carboxylated graphene sheet, and graphene is a graphene sheet produced by chemical vapor deposition;

Preparation of polyurethane adhesive: It is prepared from the invention patent 201510974180.8, a method for preparing a transparent matte water-based polyurethane emulsion and Example 1 of the transparent matte water-based polyurethane emulsion prepared by this method.

The preparation method of described antibacterial agent is: 5-hydroxytryptophan 10g, homatropine hydrobromide 3g and 2-bromo-2-nitro-1,3-propanol 2g join in the there-necked flask, 60 Stir the reaction at ℃ for 1h, then add 1g of 1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid, stir the reaction at 70°C for 1h, then add 2,3-pyrazine di 1g of carboxylic acid, 1g of aluminum sulfate, 15g of water, 2g of lithium diisopropylamide and 1.2g of 2-hydroxypropanetricarboxylic acid, stirred and reacted at 65°C for 2h, and vacuum-dried at 45°C for 1h to obtain the antibacterial agent .

The preparation method of substance A is as follows: 15g of methyl cyclohexyl propionate, 12g of hydroxyethyl acrylate and 0.5g of p-toluenesulfonic acid were subjected to transesterification at 90°C for 1 hour, and then 1.3g of 2-hydroxyethylamine and acrylamide were added. 1.4g and 1.3g of 3-aminopropyltrihydroxysilane, 1h at 80°C, then add 1g of benzyl chloride (benzyl chloride) and 1.2g of trimethylolpropane, react at 60°C for 1h, dry at 40°C , get substance A.

Example 2

The preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric is characterized in that:

(1) Preparation of modified coconut peat products: add 44.5g of modified coconut peat that has been crushed to 1-2mm into 32g of diethylaluminum hypophosphite, 3.1g of diethylenetriaminepentaacetic acid, and then add 180ml of water , stirred and reacted at 95°C for 2h, then added 0.7g of potassium hydrogen tartrate, 2.6g of diethylenetriaminepentaacetic acid, reacted at 60°C for 2h, then added 0.5g of 4-acetoxystyrene and tetraalkylammonium fluoride 6.2g, react at 70°C for 3h, stand still for 0.6h, and dry at 105°C for 2h to obtain the modified coconut bran product.

(2) Preparation of modified cotton textile fibers: immerse 44.7g of pure cotton spunlaced nonwoven fabric in 70g of 5% formic acid aqueous solution by mass fraction, and soak for 90min at 60°C, take out the cotton textile fibers, and put them in a concentration of 15% 60g of acetic acid aqueous solution, take it out after 150min, then wash 5 times with 100ml of ethanol and water mixed solution with a volume ratio of 70:30, and dry;

(3) Preparation of hygroscopic and breathable spunlace woven materials: Disperse 0.8g of sodium alginate, 0.7g of chitosan, and 0.6g of Pingpingjiao into 160g of distilled water, mix and stir at 60°C for 50min, and add to step (2) Modified cotton textile fiber and 1.6g antibacterial agent, soaked for 90min, took out, then soaked in 3-hydroxyphenylacetic acid 7g and trifluoroacetic anhydride 80g water, reacted for 3.5h, dried at 100°C for 40min, washed 5 times with water, and dried Can;

(4) Preparation of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric: 15g of modified coconut bran product obtained in step (1), 0.05g of carboxylated graphene sheet, 11.6g of polyurethane adhesive and substance A2.1g is evenly sprinkled on the surface of the hygroscopic and breathable spunlace woven material obtained in step (3), and the obtained hygroscopic and breathable spunlace woven material is folded in half, flattened, and placed in an oven at 50°C for 4 hours of heat preservation reaction. , breathable, antibacterial polyurethane synthetic leather spunlace non-woven fabric.

Carboxylated graphene sheet: Graphene 0.012g sheet was added to concentrated sulfuric acid 400ml, 4-triphenylamine borate 0.3g and 3,4,5-trifluorophenylboronic acid 0.3g and mixed, the reaction temperature was 80°C, in Condensate and reflux in an ultrasonic cleaner with an ultrasonic power of 500W and an ultrasonic frequency of 100KHz for 2 hours, dilute with 450mL deionized water after ultrasonication, and then filter with a microporous membrane with a diameter of 0.2μm, and wash repeatedly with deionized water until neutral. Finally, bake at 80°C for 8 hours, and grind to a fine powder to obtain a carboxylated graphene sheet, and graphene is a graphene sheet produced by chemical vapor deposition;

Preparation of polyurethane adhesive: It is prepared from the invention patent 201510974180.8, a method for preparing a transparent matte water-based polyurethane emulsion and Example 1 of the transparent matte water-based polyurethane emulsion prepared by this method.

The preparation method of described antibacterial agent is: 5-hydroxytryptophan 10g, homatropine hydrobromide 4g and 2-bromo-2-nitro-1,3-propanol 3g join in the there-necked flask, 60 Stir the reaction at ℃ for 2h, then add 3g of 1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid, stir the reaction at 70°C for 3h, then add 2,3-pyrazine di 2g of carboxylic acid, 2g of aluminum sulfate, 30g of water, 3g of lithium diisopropylamide and 1.2g of 2-hydroxypropanetricarboxylic acid, stirred and reacted at 65°C for 3h, and vacuum-dried at 45°C for 1h to obtain the antibacterial agent .

The preparation method of substance A is: 15g of methyl cyclohexyl propionate, 12g of hydroxyethyl acrylate and 0.5g of p-toluenesulfonic acid were subjected to transesterification at 120°C for 2 hours, and then 1.3g of 2-hydroxyethylamine and acrylamide were added. 1.4g and 1.3g of 3-aminopropyltrihydroxysilane, reacted at 110°C for 2h, then added 2g of benzyl chloride (benzyl chloride) and 1.6g of trimethylolpropane, dried at 40°C for 2h at 70°C , get substance A.

Example 3

The preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric is characterized in that:

(1) Preparation of modified coconut peat products: add 44.5g of modified coconut peat that has been crushed to 1-2mm into 32g of diethylaluminum hypophosphite, 3.1g of diethylenetriaminepentaacetic acid, and then add 180ml of water , stirred and reacted at 95°C for 2h, then added 0.7g of potassium hydrogen tartrate, 2.6g of diethylenetriaminepentaacetic acid, reacted at 60°C for 2h, then added 0.5g of 4-acetoxystyrene and tetraalkylammonium fluoride 6.2g, react at 70°C for 3h, stand still for 0.6h, and dry at 105°C for 2h to obtain the modified coconut bran product.

(2) Preparation of modified cotton textile fibers: immerse 44.7g of pure cotton spunlace nonwoven fabric in 70g of 5% formic acid aqueous solution by mass fraction, and soak for 90min at 60°C, take out the cotton textile fibers, and put them in a concentration of 15% 60g of acetic acid aqueous solution, take it out after 150min, then wash 5 times with 100ml of ethanol and water mixed solution with a volume ratio of 70:30, and dry;

(3) Preparation of hygroscopic and breathable spunlace woven materials: Disperse 0.8g of sodium alginate, 0.7g of chitosan, and 0.6g of sodium carboxymethyl cellulose into 160g of distilled water, mix and stir at 60°C for 50min, add step (2) Modified cotton textile fiber and 1.6g of antibacterial agent, soaked for 90min, taken out, then reacted in 7g of trimethylhydroxyethylpropylenediamine and 80g of trifluoroacetic anhydride for 3.5h, dried at 100°C for 20min, washed with water 4 times, just dry;

(4) Preparation of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric: 15g of modified coconut bran product obtained in step (1), 0.05g of carboxylated graphene sheet, 11.6g of polyurethane adhesive and substance A2.1g is evenly sprinkled on the surface of the hygroscopic and breathable spunlace woven material obtained in step (3), and the obtained hygroscopic and breathable spunlace woven material is folded in half, flattened, and placed in a 50°C oven to keep warm for 3 hours to obtain moisture absorption. , breathable, antibacterial polyurethane synthetic leather spunlace non-woven fabric.

Carboxylated graphene sheet: Graphene 0.012g sheet was added to concentrated sulfuric acid 400ml, 4-triphenylamine borate 0.3g and 3,4,5-trifluorophenylboronic acid 0.3g and mixed, the reaction temperature was 80°C, in Condensate and reflux in an ultrasonic cleaner with an ultrasonic power of 500W and an ultrasonic frequency of 100KHz for 2 hours, dilute with 450mL deionized water after ultrasonication, and then filter with a microporous membrane with a diameter of 0.2μm, and wash repeatedly with deionized water until neutral. Finally, bake at 80°C for 8 hours, and grind to a fine powder to obtain a carboxylated graphene sheet, and graphene is a graphene sheet produced by chemical vapor deposition;

Preparation of polyurethane adhesive: It is prepared from the invention patent 201510974180.8, a method for preparing a transparent matte water-based polyurethane emulsion and Example 1 of the transparent matte water-based polyurethane emulsion prepared by this method.

The preparation method of the described antibacterial agent is: 10g of 5-hydroxytryptophan, 3.5g of homatropine hydrobromide and 2.5g of 2-bromo-2-nitro-1,3-propanol are added in a three-necked flask , stirred at 60°C for 1.5h, then added 2g of 1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid, stirred at 70°C for 2h, then added 2,3- 1.5g of pyrazine dicarboxylic acid, 1.5g of aluminum sulfate, 22g of water, 2.5g of lithium diisopropylamide and 1.2g of 2-hydroxypropanetricarboxylic acid, stirred and reacted at 65°C for 2h, then vacuum-dried at 45°C for 1h, Obtain said antibacterial agent.

The preparation method of substance A is as follows: 15g of methyl cyclohexyl propionate, 12g of hydroxyethyl acrylate and 0.5g of p-toluenesulfonic acid were subjected to transesterification at 110°C for 1 hour, and then 1.3g of 2-hydroxyethylamine and acrylamide were added. 1.4g and 1.3g of 3-aminopropyltrihydroxysilane, at 80°C for 1h, then add 1g of benzyl chloride (benzyl chloride) and 1.2g of trimethylolpropane, at 60°C for 1h, dry at 40°C, Get substance A.

Example 4

The preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric is characterized in that:

(1) Preparation of modified coconut peat products: add 44.5g of modified coconut peat that has been crushed to 1-2mm into 32g of diethylaluminum hypophosphite, 3.1g of diethylenetriaminepentaacetic acid, and then add 180ml of water , stirred and reacted at 95°C for 1.5h, then added 0.7g of potassium hydrogen tartrate, 2.6g of diethylenetriaminepentaacetic acid, reacted at 60°C for 2h, then added 0.5g of 4-acetoxystyrene and tetraalkyl fluoride Ammonium 6.2g, react at 70°C for 2h, stand still for 0.6h, and dry at 105°C for 2h to obtain the modified coconut bran product.

(2) Preparation of modified cotton textile fibers: immerse 44.7g of pure cotton spunlace nonwoven fabric in 70g of 5% formic acid aqueous solution with a mass fraction of 40°C for 60min, take out the cotton textile fibers, and put them in a concentration of 15% 60g of acetic acid aqueous solution, take it out after 90min, then wash 4 times with 100ml of ethanol and water mixed solution with a volume ratio of 70:30, and dry;

(3) Preparation of hygroscopic and breathable spunlace woven materials: Disperse 0.8g of sodium alginate, 0.7g of chitosan, and 0.6g of diacetyl tartrate monoglyceride DATEM into 160g of distilled water, mix and stir at 60°C for 50min, add Step (2) Modified cotton textile fiber and 1.6g of antibacterial agent, soaked for 60min, took out, then soaked in water of 7g of hydroxyethylacrylamide and 80g of trifluoroacetic anhydride, reacted for 2h, dried at 100°C for 30min, washed 4 times with water, Just dry;

(4) Preparation of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric: 15g of modified coconut bran product obtained in step (1), 0.05g of carboxylated graphene sheet, 11.6g of polyurethane adhesive and substance A2.1g is evenly sprinkled on the surface of the hygroscopic and breathable spunlace woven material obtained in step (3), and the obtained hygroscopic and breathable spunlace woven material is folded in half, flattened, and placed in a 50°C oven to keep warm for 3 hours to obtain moisture absorption. , breathable, antibacterial polyurethane synthetic leather spunlace non-woven fabric.

Carboxylated graphene sheet: Graphene 0.012g sheet was added to concentrated sulfuric acid 400ml, 4-triphenylamine borate 0.3g and 3,4,5-trifluorophenylboronic acid 0.3g and mixed, the reaction temperature was 80°C, in Condensate and reflux in an ultrasonic cleaner with an ultrasonic power of 500W and an ultrasonic frequency of 100KHz for 2 hours, dilute with 450mL deionized water after ultrasonication, and then filter with a microporous membrane with a diameter of 0.2μm, and wash repeatedly with deionized water until neutral. Finally, bake at 80°C for 8 hours, and grind to a fine powder to obtain a carboxylated graphene sheet, and graphene is a graphene sheet produced by chemical vapor deposition;

Preparation of polyurethane adhesive: It is prepared from the invention patent 201510974180.8, a method for preparing a transparent matte water-based polyurethane emulsion and Example 1 of the transparent matte water-based polyurethane emulsion prepared by this method.

The preparation method of the described antibacterial agent is: 10g of 5-hydroxytryptophan, 3.5g of homatropine hydrobromide and 2.5g of 2-bromo-2-nitro-1,3-propanol are added in a three-necked flask , stirred at 60°C for 1.5h, then added 2g of 1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid, stirred at 70°C for 2h, then added 2,3- 1.5g of pyrazine dicarboxylic acid, 1.5g of aluminum sulfate, 22.5g of water, 2.5g of lithium diisopropylamide and 1.2g of 2-hydroxypropanetricarboxylic acid, stirred and reacted at 65°C for 2.5h, and dried under vacuum at 45°C 1h, to obtain the antibacterial agent.

The preparation method of substance A is as follows: 15g of methyl cyclohexyl propionate, 12g of hydroxyethyl acrylate and 0.5g of p-toluenesulfonic acid were subjected to transesterification at 105°C for 1.5h, and then 1.3g of 2-hydroxyethylamine, propylene Amide 1.4g and 3-aminopropyltrihydroxysilane 1.3g, 1.5h at 95°C, then add benzyl chloride (benzyl chloride) 1.5g and trimethylolpropane 1.4g, 1.5h at 65°C, 40°C Drying at a lower temperature yields substance A.

Example 5

The preparation method of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric is characterized in that:

(1) Preparation of modified coconut peat products: add 44.5g of modified coconut peat that has been crushed to 1-2mm into 32g of diethylaluminum hypophosphite, 3.1g of diethylenetriaminepentaacetic acid, and then add 180ml of water , stirred and reacted at 95°C for 1.5h, then added 0.7g of potassium hydrogen tartrate, 2.6g of diethylenetriaminepentaacetic acid, reacted at 60°C for 2h, then added 0.5g of 4-acetoxystyrene and tetraalkyl fluoride Ammonium 6.2g, react at 70°C for 1h, stand still for 0.6h, and dry at 105°C for 2h to obtain the modified coconut bran product.

(2) Preparation of modified cotton textile fibers: immerse 44.7g of pure cotton spunlaced nonwoven fabric in 70g of 5% formic acid aqueous solution by mass fraction, soak for 70min at 60°C, take out the cotton textile fibers, and put them in a concentration of 15% 60g of acetic acid aqueous solution, take it out after 70min, then wash 4 times with 100ml of ethanol and water mixed solution with a volume ratio of 70:30, and dry;

(3) Preparation of hygroscopic and breathable spunlace woven materials: Disperse 0.8g of sodium alginate, 0.7g of chitosan, and 0.6g of sodium carboxymethyl cellulose into 160g of distilled water, mix and stir at 60°C for 50min, add step (2) Modified cotton textile fiber and 1.6g of antibacterial agent, soaked for 40min, took out, then soaked in 7g of 3,4-dihydroxyphenylacetic acid and 80g of trifluoroacetic anhydride in water, reacted for 1h, dried at 100°C for 20min, washed with water for 4 times, just dry;

(4) Preparation of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric: 15g of modified coconut bran product obtained in step (1), 0.05g of carboxylated graphene sheet, 11.6g of polyurethane adhesive and substance A2.1g is evenly sprinkled on the surface of the hygroscopic and breathable spunlace woven material obtained in step (3), and the obtained hygroscopic and breathable spunlace woven material is folded in half, flattened, and placed in a 50°C oven to keep warm for 2 hours to obtain moisture absorption. , breathable, antibacterial polyurethane synthetic leather spunlace non-woven fabric.

Carboxylated graphene sheet: Graphene 0.012g sheet was added to concentrated sulfuric acid 400ml, 4-triphenylamine borate 0.3g and 3,4,5-trifluorophenylboronic acid 0.3g and mixed, the reaction temperature was 80°C, in Condensate and reflux in an ultrasonic cleaner with an ultrasonic power of 500W and an ultrasonic frequency of 100KHz for 2 hours, dilute with 450mL deionized water after ultrasonication, and then filter with a microporous membrane with a diameter of 0.2μm, and wash repeatedly with deionized water until neutral. Finally, bake at 80°C for 8 hours, and grind to a fine powder to obtain a carboxylated graphene sheet, and graphene is a graphene sheet produced by chemical vapor deposition;

Preparation of polyurethane adhesive: It is prepared from the invention patent 201510974180.8, a method for preparing a transparent matte water-based polyurethane emulsion and Example 1 of the transparent matte water-based polyurethane emulsion prepared by this method.

The preparation method of described antibacterial agent is: 5-hydroxytryptophan 10g, homatropine hydrobromide 3g and 2-bromo-2-nitro-1,3-propanol 3g join in the there-necked flask, 60 Stir the reaction at ℃ for 2h, then add 3g of 1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid, stir the reaction at 70°C for 3h, then add 2,3-pyrazine di 2g of carboxylic acid, 2g of aluminum sulfate, 15g of water, 2g of lithium diisopropylamide and 1.2g of 2-hydroxypropanetricarboxylic acid, stirred and reacted at 65°C for 3h, and vacuum-dried at 45°C for 1h to obtain the antibacterial agent .

The preparation method of substance A is: 15g of methyl cyclohexyl propionate, 12g of hydroxyethyl acrylate and 0.5g of p-toluenesulfonic acid were subjected to transesterification at 90°C for 1.5h, and then 1.3g of 2-hydroxyethylamine, propylene Amide 1.4g and 3-aminopropyltrihydroxysilane 1.3g, 1.5h at 110°C, then add benzyl chloride (benzyl chloride) 1.2g and trimethylolpropane 1.3g, 65°C for 2h, 40°C Dry to obtain substance A.

The liquid absorption rate uses the sieve method to test the amount of liquid absorbed in 1 hour (refer to Zhang Fushun’s paper "Study on the Liquid Absorption Rate of Super Absorbent Resin and Its Measurement Method" published in Polymer Science and Engineering), and the air permeability refers to the national standard GB/T5453 -1997 "Determination of Air Permeability of Textile Fabrics", each sample is tested 5 times, and the average value is taken;

Table 1 Test data of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwovens

Example 1 Example 2 Example 3 Example 4 Example 5 Air flow (mm/s) 441 439 426 411 401 Liquid absorption rate/% 603 612 623 615 606 Escherichia coli/% 1.7 2.4 2.6 7.9 4.6 Aspergillus niger/% 6.4 4.7 6.4 4.9 5.5 Breaking strength/MPa 24.4 31.4 26.7 28.9 27.8 Elongation at break/% 317 356 368 358 378

As can be seen from Table 1, the air permeability and liquid absorption rate of the present invention are relatively high after modification, which shows that the modified material is used in the present invention to obviously improve the air permeability and liquid absorption rate of the material.

Table 2 Test data (adding modified coconut peat products, without adding 4-acetoxystyrene or tetraalkylammonium fluoride)

As can be seen from Table 2, adding coconut bran products without adding 4-acetoxystyrene or tetraalkylammonium fluoride, it is found that 4-acetoxystyrene or tetraalkylammonium fluoride assist coconut The bran product increases the liquid absorption of cotton.

Table 3 Test data of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwovens (without adding TFA)

The comparative example uses Example 1 of 201711233692.4 (the same below), the antibacterial effect without adding trifluoroacetic anhydride decreases, and the antibacterial effect of trifluoroacetic anhydride lasts.

Table 4 Test data of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric (without 2-hydroxypropanetricarboxylic acid)

The antibacterial effect of not adding 2-hydroxypropanetricarboxylic acid decreased (Example 1, Escherichia coli 48.9, Aspergillus niger 55.6;).

Table 5 Test data of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric (without adding lithium diisopropylamide)

The antibacterial effect decreased without adding lithium diisopropylamide.

Table 6 Test data of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric (without substance A)

The dispersibility of the polyurethane adhesive is improved without adding substance A.

Table 7 Test data of hygroscopic, breathable and antibacterial polyurethane synthetic leather spunlaced nonwoven fabric (with substance A added, without benzyl chloride added)

Example 1 Example 2 Example 3 Example 4 Example 5 Air flow (mm/s) 312 345 299 322 307

The addition of substance A improves the dispersibility of the polyurethane adhesive, and the addition of benzyl chloride has a great influence on the air permeability of the polyurethane synthetic leather spunlaced nonwoven fabric, and its air permeability decreases.

Claims (1)

1. the modified coconut bran product preparation method required for the preparation method of the hygroscopic, breathable, antibacterial polyurethane synthetic leather spunlaced non-woven fabric, is characterized in that: Add 44.5g of modified coconut peat crushed to 1-2mm into 32g of aluminum diethylphosphinate and 3.1g of diethylenetriaminepentaacetic acid, then add 180ml of water, and stir at 95°C for 1~2h , then add 0.7g of potassium hydrogen tartrate, 2.6g of diethylenetriaminepentaacetic acid, react at 60°C for 2h, then add 0.5g of 4-acetoxystyrene and 6.2g of tetraalkylammonium fluoride, react at 70°C for 1 ~ 3h, stand still for 0.6h, and dry at 105°C for 2h to obtain the modified coconut bran product.