CN108929446B - Graphene composite master batch, modified fiber, superfine fiber leather and preparation method and application thereof - Google Patents

Graphene composite master batch, modified fiber, superfine fiber leather and preparation method and application thereof Download PDF

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CN108929446B
CN108929446B CN201710378098.8A CN201710378098A CN108929446B CN 108929446 B CN108929446 B CN 108929446B CN 201710378098 A CN201710378098 A CN 201710378098A CN 108929446 B CN108929446 B CN 108929446B
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graphene
master batch
preparation
base material
graphene composite
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CN108929446A (en
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吕冬生
孙海波
王双成
马军强
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Shandong Shengquan New Material Co Ltd
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Shandong Shengquan New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Abstract

Graphene composite master batches, modified fibers, superfine fiber leather and preparation method and application thereof. The invention relates to a preparation method of a graphene composite master batch, which comprises the following steps: (1) dividing the base material into n parts, wherein the mass of the (n + 1) th part of base material is less than 10 times of that of the nth part of base material; (2) mixing the 1 st part of base material with the graphene material to obtain 1 st mixed master batch; (3) mixing the (n + 1) th base material with the nth mixed master batch to obtain the (n + 1) th mixed master batch, namely the graphene composite master batch; wherein n is a positive integer. According to the invention, by adjusting the mixing mode of the graphene and the base material, the master batch with the graphene material uniformly dispersed is obtained, the graphene agglomeration phenomenon is reduced, and the antibacterial property and far infrared performance of the master batch are improved.

Description

Graphene composite master batch, modified fiber, superfine fiber leather and preparation method and application thereof
Technical Field
The invention belongs to the field of synthetic leather, and particularly relates to a graphene composite master batch and a preparation method thereof, a modified fiber prepared from the graphene composite master batch and a preparation method thereof, superfine fiber leather prepared from the modified fiber and a preparation method and application thereof.
Background
Because the resources of natural leather are limited, along with the progress of scientific technology and the improvement of the living standard of people, the development of high-quality simulation leather to meet the market demand becomes a problem to be solved urgently. The artificial leather production has been in industrial production for decades, and products thereof are continuously updated with the continuous application of various new materials. Superfine fiber synthetic leather (abbreviated as "microfiber leather") has been rapidly developed as third-generation artificial synthetic leather. The main raw materials for manufacturing the microfiber leather are bundle-shaped ultrafine fibers and polyurethane. The microfiber leather product is inspected and practiced in many aspects, and has high tearing strength and tensile strength, good folding resistance, good simulation and easy surface cleaning. However, the antibacterial activity and antibacterial property of the microfiber leather have certain defects, and particularly, when the microfiber leather is used as a raw material for manufacturing high-grade products such as leather shoes, leather clothing, sofas, automotive interiors and the like, the surfaces of the microfiber leather are mildewed and cracked after being used for a long time, so that the microfiber leather cannot be used and loses value. Therefore, a microfiber leather capable of inhibiting harmful bacteria is needed to facilitate the life of people.
The main bacteriostatic agents at present are inorganic metal compounds such as silver-carrying zeolite and silver-carrying silicate, organic metal compounds such as quaternary ammonium salts, pyridines and imidazoles, and natural organic substances such as chitosan. There are two main methods for loading bacteriostatic agents onto leather: direct addition and post-finishing. However, the bacteriostatic measures have certain defects, and because the bacteriostatic agent is added instead of the substance, the bacteriostatic substance can gradually fall off along with the long-term use of the product, so that the product loses the bacteriostatic function. Meanwhile, the use of some heavy metal ions can cause certain pollution to the environment.
How to obtain synthetic leather with antibacterial property or fiber materials or master batches for synthetic leather is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a preparation method of graphene composite master batch, which comprises the following steps:
(1) dividing the base material into n parts, wherein the mass of the (n + 1) th part of base material is less than 10 times of that of the nth part of base material;
(2) mixing the 1 st part of base material with the graphene material to obtain 1 st mixed master batch;
(3) mixing the (n + 1) th base material with the nth mixed master batch to obtain the (n + 1) th mixed master batch, namely the graphene composite master batch;
where n is a positive integer, e.g., 1, 2, 3, 4, 5, etc.
According to the invention, the base material is divided into n parts, and the n +1 part of base material is mixed with the graphene material in sequence, and the mass of the n +1 part of base material is limited to be less than 10 times of that of the n part of base material, so that the graphene material can be uniformly dispersed, the agglomeration of graphene is reduced, and the value of graphene is exerted to the greatest extent.
As one of the preferable technical proposal, the preparation method comprises the following steps:
(1) dividing the base material into 2 parts, wherein the mass of the 2 nd part of the base material is less than 10 times of that of the 1 st part of the base material;
(2) mixing the 1 st part of base material with the graphene material to obtain 1 st mixed master batch;
(3) and mixing the 2 nd part of base material with the 1 st mixed master batch to obtain the 2 nd mixed master batch, namely the graphene composite master batch.
According to the invention, the base material is divided into 2 parts, and the mass of the 2 nd part of base material is limited to be less than 10 times of the mass of the 1 st part of base material, so that the base material and the graphene material can be uniformly mixed.
Preferably, the mass ratio of the graphene material in the step (2) to the 1 st part of the base material is 1: 10-100, such as 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, and the like.
Preferably, the step (2) of mixing the 1 st part of the base material with the graphene material includes the following steps:
(2a) mixing the 1 st part of base material with a graphene material with the particle size D90 being less than or equal to 1 mu m;
(2b) and (3) mixing the mixed material obtained in the step (2a) with a graphene material with the particle size of more than 1 mu m and less than or equal to D90 and less than or equal to 8 mu m.
The graphene material with the particle size D90 being not more than 1 μm is firstly mixed with the 1 st base material, and then is mixed with the graphene material with the particle size D90 being not more than 8 μm, so that the distribution of the graphene with different particle sizes is more uniform, namely the number of the graphene with different particle sizes distributed in the same range is the same.
Preferably, the mass ratio of the graphene material with the particle size of D90 being less than or equal to 1 μm to the graphene material with the particle size of 1 μm < D90 being less than or equal to 8 μm is 1: 1-5, such as 1:2, 1:3, 1:4, and the like.
Preferably, the graphene material is 5 to 10 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, and the like, based on 100 parts by weight of the total mass of the graphene composite mother particles.
Preferably, the graphene material comprises any 1 or combination of at least 2 of graphene and graphene derivatives, preferably any 1 or combination of at least 2 of reduced graphene oxide, graphene prepared from biomass raw materials, graphene obtained by exfoliating graphite, and graphene obtained by vapor deposition.
Preferably, the base material comprises any 1 or at least 2 of polypropylene master batch, polyester master batch, chinlon master batch, spandex master batch and acrylic master batch.
The second purpose of the invention is to provide the graphene composite master batch, which is prepared by the preparation method of the second purpose.
The invention also provides a preparation method of the modified fiber, which comprises the following steps:
and mixing the graphene composite master batches of the second purpose with the blank slices to obtain a mixture, and then spinning.
Preferably, the components of the mixture comprise the following components in parts by weight:
5-15 parts of graphene composite master batch
85-95 parts of blank slices
The sum of the components of the mixture is 100 parts by weight.
Preferably, the particle size of the second-purpose graphene composite mother particles is not more than the particle size of the blank slice, and the ratio of the particle sizes of the second-purpose graphene composite mother particles to the blank slice is 1:2 to 10, for example, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, and the like.
The fourth purpose of the invention is to provide a preparation method of sea-island superfine fiber, which comprises the following steps:
and adding the graphene composite master batch into the island component to obtain the island component mixed with the graphene composite master batch, then melting and mixing the sea component and the island component mixed with the graphene composite master batch in a melt spinning process, and then spinning to obtain the island-in-sea fiber.
Preferably, the island component mixed with the graphene composite master batch comprises the following components in parts by weight:
5-15 parts of graphene composite master batch
85-95 parts of island component
The sum of the components of the mixture is 100 parts by weight;
preferably, the particle size of the second graphene composite mother particle is not more than the particle size of the island component, and the ratio of the particle size of the second graphene composite mother particle to the particle size of the island component is 1:2 to 10, for example, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, and the like.
Preferably, the mixing ratio of the sea component to the island component mixed with the graphene composite master batch is 30% -40% to 70% -60%, for example 31% to 69%, 32% to 68%, 33% to 67%, 34% to 66%, 35% to 65%, 36% to 64%, 37% to 63%, 38% to 62%, 39% to 61%, and the like.
Preferably, the island number of the island-in-sea microfiber is 37 islands.
Optionally, after the "spinning" step, the steps of oiling, drawing, drying are performed.
The fifth purpose of the invention is to provide a sea-island ultrafine fiber prepared by the preparation method of the fourth purpose.
The invention aims at providing a preparation method of superfine fiber leather, which comprises the following steps:
(I) preparing a nonwoven fabric from the island-in-sea microfiber of claim 7;
(II) dipping the non-woven fabric obtained in the step (I) into a polyurethane solution;
(III) solidifying the non-woven fabric dipped in the polyamide solution in the step (II) in a dimethylformamide aqueous solution, and removing the sea component in the island-in-sea type superfine fiber by alkali decrement after washing;
(IV) drying the non-woven fabric treated in the step (III) to obtain superfine fiber leather;
preferably, the concentration of the aqueous solution of dimethylformamide in step (III) is 20 to 50 wt%, such as 22 wt%, 25 wt%, 27 wt%, 28 wt%, 32 wt%, 35 wt%, 37 wt%, 38 wt%, 42 wt%, 45 wt%, 47 wt%, 48 wt%, etc.
Preferably, the solidification temperature is 20-50 deg.C, such as 22 deg.C, 25 deg.C, 27 deg.C, 32 deg.C, 35 deg.C, 38 deg.C, 42 deg.C, 48 deg.C, etc., and the time is 30-60 min, such as 35min, 40min, 45min, 55min, 60min, etc.
Preferably, the temperature of the water washing is 40 to 70 ℃, such as 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ and the like.
Preferably, the alkali-decreasing manner for removing the sea component in the sea-island type microfiber comprises:
and immersing the washed non-woven fabric into NaOH solution with the concentration of 15-30 g/L and the temperature of 80-100 ℃, and treating the base material for 30-60 min.
The seventh purpose of the invention is to provide superfine fiber leather which is prepared by the preparation method of the sixth purpose.
The invention aims to provide application of superfine fiber leather, and the superfine fiber leather is used for preparing shoes, cases, furniture or automotive interiors.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method, the master batch with the uniformly dispersed graphene material is obtained by adjusting the mixing mode of the graphene and the base material, so that the graphene agglomeration phenomenon is reduced, and the antibacterial property and far infrared performance of the master batch are improved;
(2) further, graphene with different particle sizes is added to the base material in batches, so that the uniform distribution of graphene materials with different particle sizes is obtained, and the uniform distribution of the graphene materials in the master batch is further improved;
(3) according to the invention, the superfine fiber is prepared by the base material mixed with the graphene material, so that the superfine fiber has excellent antibacterial performance, and after the synthetic leather is prepared from the superfine fiber and polyurethane, the phenomena of mildew and cracking caused by long-time use can be relieved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The graphene materials of examples 1 to 8 and comparative example 1 are graphene prepared by using biomass as a raw material, the preparation method can refer to the method of patent publication No. CN 104016341 example 1, and the base material is nylon masterbatch.
Example 1
A preparation method of graphene composite master batches comprises the following steps:
(1) dividing the base material into 2 parts, a first part of base material is 1kg, and a second part of base material is 5 kg;
(2) mixing the 1 st part of base material with 100g of graphene material to obtain 1 st mixed master batch;
(3) and mixing the 2 nd part of base material with the 1 st mixed master batch to obtain the 2 nd mixed master batch, namely the graphene composite master batch.
Example 2
A preparation method of graphene composite master batches comprises the following steps:
(1) dividing the base material into 2 parts, a first part of base material is 1kg, and a second part of base material is 5 kg;
(2a) mixing the 1 st part of base material with 30g of graphene material with the particle size D90 of 1 mu m;
(2b) mixing the mixed material obtained in the step (2a) with 70g of graphene material with the particle size D90 of 8 mu m;
(3) and mixing the 2 nd part of base material with the 1 st mixed master batch to obtain the 2 nd mixed master batch, namely the graphene composite master batch.
Example 3
A preparation method of graphene composite master batches comprises the following steps:
(1) dividing the base material into 2 parts, a first part of base material is 1kg, and a second part of base material is 5 kg;
(2a) mixing the 1 st part of base material with 17g of graphene material with the particle size D90 of 0.5 mu m;
(2b) mixing the mixed material obtained in the step (2a) with 83g of graphene material with the particle size D90 of 5 microns;
(3) and mixing the 2 nd part of base material with the 1 st mixed master batch to obtain the 2 nd mixed master batch, namely the graphene composite master batch.
Example 4
A preparation method of graphene composite master batches comprises the following steps:
(1) dividing the base material into 2 parts, a first part of base material is 1kg, and a second part of base material is 5 kg;
(2a) mixing the 1 st part of base material with 50g of graphene material with the particle size D90 of 0.1 mu m;
(2b) mixing the mixed material obtained in the step (2a) with 50g of graphene material with the particle size D90 of 3 mu m;
(3) and mixing the 2 nd part of base material with the 1 st mixed master batch to obtain the 2 nd mixed master batch, namely the graphene composite master batch.
Example 5
A preparation method of graphene composite master batches comprises the following steps:
(1) dividing the base material into 2 parts, a first part of base material is 1kg, and a second part of base material is 5 kg;
(2a) mixing the 1 st part of base material with 50g of graphene material with the particle size D90 of 0.3 mu m;
(2b) mixing the mixed material obtained in the step (2a) with 100g of graphene material with the particle size D90 of 8 mu m;
(3) and mixing the 2 nd part of base material with the 1 st mixed master batch to obtain the 2 nd mixed master batch, namely the graphene composite master batch.
Example 6
The preparation method of the graphene composite master batch is different from that of the embodiment 1 in that the addition amount of the graphene material in the step (2) is 50 g.
Example 7
The preparation method of the graphene composite master batch is different from that of the embodiment 1 in that the addition amount of the graphene material in the step (2) is 80 g.
Example 8
The preparation method of the graphene composite master batch is different from that of the embodiment 1 in that in the step (1), the first part of the base material is 1kg, and the second part of the base material is 8 kg.
Comparative example 1
The preparation method of the graphene composite master batch is different from that of the embodiment 1 in that in the step (1), the first part of the base material is 1kg, and the second part of the base material is 12 kg.
Example 9
The difference between the preparation method of the graphene composite master batch and the embodiment 1 is that the base material is the polyester master batch.
Example 10
The preparation method of the graphene composite master batch is different from that of the embodiment 1 in that the graphene material is graphene oxide, and the base material is polyester master batch.
Application example
The preparation method of the superfine fiber comprises the following steps:
(1) and (3) slicing and drying:
respectively slicing and drying the sea component and the island component, wherein the island component requires 30-50 ppm of water content, and the sea component requires 30-100 ppm of water content;
(2) melting and spinning:
respectively putting the dried sea component slices and the dried island component slices into respective spinning storage tanks through a feeding system, simultaneously respectively adding the graphene composite master batches of examples 1-10 and comparative example 1 into the island components, feeding the island components into respective screw extruders through a feeding system, heating, melting and extruding the island components, forming spinning melt through respective melt filters, and finally feeding the island components into a spinning box for spinning;
the spinning melt entering the spinning box firstly enters respective metering pumps to carry out metering according to the proportion of sea-island components, wherein the mass ratio of the sea components to the island components is controlled to be 30 to 70 percent, the island number is 37 islands, then the spinning melt enters a composite spinning assembly, and finally the spinning melt is sprayed out by a spinneret plate to form the sea-island structure composite filament;
(3) cooling and dropping into a barrel:
cooling and forming the filaments sprayed from the spinneret plate by cross air blowing, oiling, doubling, and forming a filament barrel by a winding device;
(4) drawing and curling:
bundling tows of a certain number of filament barrels through a bundling frame, then drafting, controlling the drafting temperature at 150 ℃, then shaping through hot steam at 120 ℃, and finally curling in a curling box;
(5) drying and cutting:
and (3) loosening, drying and shaping the crimped tow, and finally cutting the dried tow into 38mm fixed island staple fibers.
Examples of production of ultrafine fiber leather
A preparation method of superfine fiber leather comprises the following steps:
(1) spinning cloth:
opening, carding and lapping the fixed island superfine fibers obtained in the application example to form a composite layer fiber web, and needling the composite layer fiber web by a plurality of subsequent needling machines to form a needled non-woven fabric;
(2) dipping:
dipping the obtained non-woven fabric in a polyurethane solution;
(3) and (3) solidification:
fully solidifying the impregnated non-woven fabric in a Dimethylformamide (DMF) water solution with the concentration of 20-50% and the temperature of 20-50 ℃ for 30-60 min;
(4) washing with water:
fully washing the synthetic leather impregnated base material in water at the temperature of 40-70 ℃;
(5) alkali decrement:
immersing the impregnated base material into NaOH solution with the concentration of 15-30 g/L and the temperature of 80-100 ℃, treating the base material for 30-60 min, removing the sea component in the figured fiber to realize the superfine fiber, and then fully washing and neutralizing;
(6) and (3) drying: and drying the neutralized base material in a hot air oven to obtain the graphene superfine fiber synthetic leather.
Performance testing
The prepared superfine fiber leather is subjected to the following performance tests:
(1) antibacterial and bacteriostatic properties: the test method is GB/T20944.3-2008 < evaluation of antibacterial performance of textiles part three: and (4) an oscillation method, which respectively determines the bacteriostasis rates of the biomass graphene modified polyamide fiber and the polyamide fiber to escherichia coli, candida albicans and staphylococcus aureus.
(2) And (3) temperature rise test, in particular to GB/T30127-2013 detection and evaluation of far infrared performance of textiles.
(3) Cracking: the test method is QB/T3812.7 leather grain surface strength and stretching height determination bursting test
The test results are shown in Table 1.
Table 1 performance test of ultrafine fiber leather using graphene composite master batches of examples and comparative examples
Figure BDA0001303178540000081
Figure BDA0001303178540000091
It can be seen from table 1 that when the base material and the graphene material are mixed in several times and the mixing amount of the next time is less than or equal to 10 of the mixing amount of the base material in the previous step, excellent antibacterial (staphylococcus aureus, escherichia coli, candida albicans) performance can be obtained, the bacteriostasis of staphylococcus aureus is over 88%, the bacteriostasis rate of escherichia coli is over 86%, the bacteriostasis rate of candida albicans is over 85%, the crack value is over 5mm, and the heating rate is over 2 ℃.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (26)

1. A preparation method of modified fiber is characterized by comprising the following steps:
(1) dividing the base material into 2 parts, wherein the mass of the 2 nd part of the base material is 5 times that of the 1 st part of the base material;
(2) mixing the 1 st part of base material with the graphene material to obtain a 1 st-time mixture;
(3) mixing the 2 nd base material with the 1 st mixed material to obtain a 2 nd mixed material, and granulating after melting to obtain graphene composite master batches;
(4) mixing the graphene composite master batch obtained in the step (3) with the blank slices to obtain a mixture, and then spinning to obtain the modified fiber;
the mass ratio of the graphene material in the step (2) to the 1 st base material is 1: 10-100.
2. The preparation method of claim 1, wherein the step (2) of mixing the 1 st part of the substrate with the graphene material comprises the following steps:
(2a) mixing the 1 st part of base material with a graphene material with the particle size D90 being less than or equal to 1 mu m;
(2b) and (3) mixing the mixed material obtained in the step (2a) with a graphene material with the particle size of more than 1 mu m and less than or equal to D90 and less than or equal to 8 mu m.
3. The preparation method of claim 2, wherein the mass ratio of the graphene material with the particle size of D90 being less than or equal to 1 μm to the graphene material with the particle size of 1 μm < D90 being less than or equal to 8 μm is 1: 1-5.
4. The preparation method according to claim 1, wherein the graphene material is 5 to 10 parts by weight based on 100 parts by weight of the total mass of the graphene composite mother particles.
5. The method of claim 1, wherein the graphene material comprises any 1 or a combination of at least 2 of graphene, graphene derivatives.
6. The method according to claim 1, wherein the graphene material includes any 1 or a combination of at least 2 of reduced graphene oxide, graphene prepared from biomass, graphene obtained by exfoliating graphite, and graphene obtained by vapor deposition.
7. The method of claim 1, wherein the substrate comprises any 1 or at least 2 of polypropylene mother particles, polyester mother particles, polyamide mother particles, spandex mother particles and acrylic mother particles.
8. The preparation method of claim 1, wherein the components of the mixture in the step (4) comprise the following components in parts by weight:
5-15 parts of graphene composite master batch
85-95 parts of blank slices
The sum of the components of the mixture is 100 parts by weight.
9. The preparation method of claim 8, wherein the particle size of the graphene composite master batch is smaller than or equal to that of the blank slice.
10. The preparation method of claim 8, wherein the ratio of the particle size of the graphene composite master batch to the particle size of the blank slice is 1: 2-10.
11. A modified fiber, which is obtained by the production method according to any one of claims 1 to 7.
12. A preparation method of sea-island superfine fiber is characterized by comprising the following steps:
adding the graphene composite master batch of the step (3) of claim 1 into the island component to obtain the island component mixed with the graphene composite master batch, then melt-mixing the sea component and the island component mixed with the graphene composite master batch in a melt spinning process, and then spinning to obtain the island-in-sea fiber.
13. The preparation method of claim 12, wherein the island component mixed with the graphene composite masterbatch comprises the following components in parts by weight:
5-15 parts of graphene composite master batch
85-95 parts of island component
The sum of the components of the mixture is 100 parts by weight.
14. The preparation method of claim 12, wherein the particle size of the graphene composite masterbatch is not larger than the particle size of the island component.
15. The preparation method of claim 12, wherein the particle size ratio of the graphene composite master batch to the island component is 1: 2-10.
16. The method of claim 12, wherein the mixing ratio of the sea component to the island component mixed with the graphene composite masterbatch is 30-40% to 70-60%.
17. The method of claim 12, wherein the sea-island type microfiber has 37 islands.
18. The method of claim 12, wherein the step of "spinning" is followed by the steps of oiling, drawing, and drying.
19. A sea-island ultrafine fiber characterized in that it is prepared by the method according to any one of claims 12 to 18.
20. The preparation method of the superfine fiber leather is characterized by comprising the following steps:
(I) preparing a nonwoven fabric from the island-in-sea microfiber of claim 19;
(II) dipping the non-woven fabric obtained in the step (I) into a polyurethane solution;
(III) solidifying the non-woven fabric dipped in the polyurethane solution in the step (II) in a dimethylformamide aqueous solution, and removing the sea component in the island-in-sea type superfine fiber by alkali decrement after washing;
and (IV) drying the non-woven fabric treated in the step (III) to obtain the superfine fiber leather.
21. The method according to claim 20, wherein the concentration of the aqueous solution of dimethylformamide in the step (III) is 20 to 50 wt%.
22. The method of claim 20, wherein the solidification temperature is 20 to 50 ℃ and the time is 30 to 60 min.
23. The method according to claim 20, wherein the temperature of the water washing is 40 to 70 ℃.
24. The method of claim 20, wherein the alkali-decreasing removal of the sea component in the island-in-sea type microfiber comprises:
and immersing the washed non-woven fabric into NaOH solution with the concentration of 15-30 g/L and the temperature of 80-100 ℃, and treating the base material for 30-60 min.
25. Superfine fiber leather prepared by the preparation method of any one of claims 20 to 24.
26. Use of the microfibre leather of claim 25, in the manufacture of shoes, bags, furniture or automotive interiors.
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