CN114164680A - Preparation method and application of durable antibacterial mildew-proof regenerated leather - Google Patents

Preparation method and application of durable antibacterial mildew-proof regenerated leather Download PDF

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CN114164680A
CN114164680A CN202111418446.2A CN202111418446A CN114164680A CN 114164680 A CN114164680 A CN 114164680A CN 202111418446 A CN202111418446 A CN 202111418446A CN 114164680 A CN114164680 A CN 114164680A
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leather
antibacterial
waterborne polyurethane
regenerated
regenerated leather
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CN114164680B (en
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谭淋
龚达开
韩颜庭
施亦东
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Sichuan University
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Sichuan University
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    • 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
    • D06N3/147—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 characterised by the isocyanates used
    • D06N3/148—(cyclo)aliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • D—TEXTILES; PAPER
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • D06N3/146—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 characterised by the macromolecular diols used
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    • 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
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
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    • 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
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—Polyurethanes
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    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
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Abstract

The invention discloses a preparation method of durable antibacterial mildew-proof regenerated leather, which comprises the following steps: dispersing leather fibers into deionized water, and then stirring to form uniform suspension; uniformly dispersing the suspension on a metal filter screen to obtain a leather fiber mat, wherein the dispersion thickness is about 1.0-2.0 mm; then pouring the antibacterial waterborne polyurethane on the surface of the leather fiber mat, and obtaining a composite material after complete permeation, wherein the dosage ratio of the leather fiber mat to the antibacterial waterborne polyurethane is 1: 0.4-3; putting the composite material into an oven at 50-80 ℃, and then performing in-situ reaction for 12-36h to obtain the antibacterial mildew-proof regenerated leather; the regenerated leather prepared by the invention is used for preparing insoles and other shoe leather products, has excellent antibacterial and mildewproof effects, is wear-resistant and has good mechanical properties, the heavy metal dissolution rate is low, new economic benefits are generated, waste is changed into valuable, and the harm to the environment is reduced.

Description

Preparation method and application of durable antibacterial mildew-proof regenerated leather
Technical Field
The invention relates to the technical field of synthetic leather production, in particular to a preparation method of durable antibacterial mildew-proof regenerated leather.
Background
Most of the existing waste leather is treated in a physical burying way, and the waste materials cannot be effectively utilized; and has the following disadvantages:
(1) the landfill disposal of these materials requires a large amount of manpower and material resources, which will greatly increase the cost required for disposing the waste materials;
(2) the waste leather is buried underground, and the chromium element which is not completely reacted in the chrome tanning process can permeate into soil and pollute underground water sources, so that huge pollution is brought to crops and drinking water which are eaten by people, and great threat is brought to the survival and environment of human beings;
(3) the waste leather can bring serious resource waste when being directly buried, and does not meet the overall target of building a resource-saving and environment-friendly society;
how to avoid the problems becomes a big problem in recycling the waste leather, and meanwhile, the regenerated leather made of the recycled waste leather has no antibacterial and mildewproof effects, and the release amount of heavy metals cannot be effectively reduced in the using process of the made product.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of durable antibacterial and mildewproof regenerated leather, so as to at least achieve the purposes of pollution-free waste leather recovery and preparation of regenerated leather with antibacterial and mildewproof properties and excellent wear resistance and mechanical properties.
The purpose of the invention is realized by the following technical scheme: a preparation method of durable antibacterial mildew-proof regenerated leather comprises the following steps:
s1, dispersing leather fibers into deionized water, and stirring to form uniform suspension;
s2, uniformly dispersing the suspension on a metal filter screen to obtain a leather fiber mat, wherein the dispersion thickness is about 1.0-2.0 mm;
s3, pouring antibacterial waterborne polyurethane on the surface of the leather fiber mat, and obtaining a composite material after complete permeation, wherein the use amount ratio of the leather fiber mat to the antibacterial waterborne polyurethane is 1: 0.4-3;
s4, putting the composite material into an oven at 50-80 ℃, and then performing in-situ action for 12-36h to obtain the antibacterial and mildewproof regenerated leather.
Further, the preparation method of the antibacterial waterborne polyurethane comprises the following steps:
s31, uniformly mixing 0.075-0.1125 part of tetrahydrofuran homopolyether and 0.02-0.03 part of N120 in parts by weight to obtain a mixed solution;
s32, dehydrating the mixed solution at 100 ℃ for 2h, then cooling to 60 ℃, and adding 0.0192-0.0288 parts of neopentyl glycol; when the temperature is reduced to 40 ℃, 0.18-0.27 part of isophorone diisocyanate is added, and 0.000584-0.000876 parts of dibutyltin dilaurate are added at the same time; then gradually raising the temperature to 85-95 ℃, and preserving the temperature for 3 hours to obtain a prepolymer;
s33, cooling the prepolymer to 40 ℃, adding a certain amount of ice water, and violently stirring to emulsify the system; then 0.000292-0.000438 parts of polyhexamethylene guanidine are quickly added, and 0.05371-0.080565 parts of ethylenediamine are dropwise added; finally reacting for 1.5-2.5h at the temperature of 30-40 ℃ to obtain the antibacterial waterborne polyurethane; the polyhexamethylene guanidine is any one of polyhexamethylene biguanide hydrochloride, polyhexamethylene monoguanidine hydrochloride and polyhexamethylene guanidine phosphate.
In the process of synthesizing the antibacterial waterborne polyurethane, the tetrahydrofuran homopolyether is used as a monomer for synthesizing the antibacterial waterborne polyurethane, and the monomers which can be selected for synthesizing the antibacterial waterborne polyurethane mainly comprise polyether dihydric alcohol and polyester dihydric alcohol; isocyanates can be both aromatic and aliphatic, such as MDI, HDI, TDI, and the like; the ethylene diamine is a chain extender, and the chain extender can be diol or diamine substances, such as ethylene diamine, butanediol and the like.
Further, the weight ratio of the leather fiber in the regenerated leather to the antibacterial waterborne polyurethane is any one of 30:70, 40:60, 50:50, 60:40 and 70:30, which are abbreviated as LF/PPU-3, LF/PPU-4, LF/PPU-5, LF/PPU-6 and LF/PPU-7 in sequence.
The antibacterial mildew-proof regenerated leather is used for preparing any one of shoe leather fabric, insoles and heat-insulating pads.
The invention takes the waste leather fiber (from leather clothing, shoes or other leather products) as the raw material, prepares the waste leather fiber into non-woven fabrics, then soaking the leather in antibacterial waterborne polyurethane, carrying out heat setting to prepare regenerated leather, wherein the lower layer of the regenerated leather mainly comprises a leather fiber material and a part of the waterborne polyurethane, the upper layer of the regenerated leather is the antibacterial waterborne polyurethane material, the antibacterial waterborne polyurethane is used as an external frame of the regenerated leather to support the whole system, meanwhile, the scattered waste leather fibers can be wrapped and made into the shape of a fixed material in a screen mesh, the waterborne polyurethane provides excellent mechanical property and wear resistance for the regenerated leather, so that the waste leather fibers can fully play the characteristics of moisture absorption and air permeability as a part of a matrix, meanwhile, the composite superposition of the antibacterial waterborne polyurethane and the waste leather fiber enables the material to better meet various requirements in the use environment of the foot pad.
The antibacterial waterborne polyurethane is prepared by a conventional three-step method (namely 'dewatering-prepolymerization-emulsification chain extension'), and is used as a filler and an adhesive to be blended with the waste leather fibers; besides physical binding force, chemical crosslinking exists between the antibacterial waterborne polyurethane and the waste leather fibers, so that the antibacterial effect of the regenerated leather is further improved; the antibacterial and mildewproof unit comprises one or more of (types of) bronopol, polymeric guanidine, nipagin esters, isothiazolinone, 2-dibromo-3-nitrilopropionamide and pyrithione, and the antibacterial and mildewproof unit exists in a molecular chain of the waterborne polyurethane through chemical bonds, so that the antibacterial performance of the antibacterial waterborne polyurethane is excellent.
The invention has the beneficial effects that:
(1) the waste leather is recycled, so that a large amount of manpower and material resources required by burying are saved, and the cost required by treating waste materials is reduced.
(2) Effectively avoids the damage of waste leather containing heavy metal chromium elements to the land and water source, and effectively protects the living environment and the self health of human beings.
(3) The waste leather is recycled to prepare the antibacterial regenerated leather with excellent mechanical property, and the regenerated leather is made into a new product, so that the waste phenomenon of resources is effectively reduced, and the utilization rate of the resources is improved; meanwhile, the new product can also generate new profit and economic value.
(4) A small amount of unreacted chromium elements in the waste leather exist in a free state, and the dissolution of the chromium elements can pollute the environment when a new product is prepared by utilizing the chromium elements.
(5) Compared with the existing foot pad material, the foot pad prepared from the regenerated leather has the advantages of antibacterial and mildew-proof effects, excellent wear resistance and mechanical properties, and effective reduction of the dissolution of heavy metal elements.
(6) The antibacterial waterborne polyurethane used in the invention is used as a new generation of antibacterial polymer, and the aqueous solution is nontoxic, colorless and odorless; the low-concentration antibacterial waterborne polyurethane prepared by the method has extremely strong capability of killing bacteria, is broad-spectrum and efficient, and has a long-term antibacterial effect; no etching effect on various materials; it contains no harmful substances such as aldehyde, iodine, and active chlorine.
Drawings
FIG. 1 is an infrared test chart of antibacterial aqueous polyurethane and common polyurethane;
FIG. 2 is a graph showing the release of chromium from reclaimed leather;
FIG. 3 is a wear resistance test chart of the recycled leather;
FIG. 4 is a tear strength test chart for recycled leather;
FIG. 5 is a test chart of antibacterial performance of the regenerated leather;
FIG. 6 is a test chart of the mildew resistance of the regenerated leather.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Example 1
A preparation method of durable antibacterial mildew-proof regenerated leather comprises the following steps:
s1, dispersing leather fibers into deionized water, and stirring to form uniform suspension;
s2, uniformly dispersing the suspension on a metal filter screen to obtain a leather fiber mat, wherein the dispersion thickness is about 1.0 mm;
s31, uniformly mixing 0.0750 parts of tetrahydrofuran homopolyether and 0.02 part of N120 in parts by weight to obtain a mixed solution;
s32, dehydrating the mixed solution at 100 ℃ for 2h, then cooling to 60 ℃, and adding 0.0192 parts of neopentyl glycol; when the temperature is reduced to 40 ℃, 0.18 part of isophorone diisocyanate is added, and 0.000584 parts of dibutyltin dilaurate is added at the same time; then gradually raising the temperature to 85 ℃, and preserving the temperature for 3 hours to obtain a prepolymer;
s33, cooling the prepolymer to 40 ℃, adding a certain amount of ice water, and violently stirring to emulsify the system; thereafter, 0.000292 parts of polyhexamethylene guanidine were rapidly added, and thereafter 0.0537 parts of ethylenediamine were dropwise added; finally reacting for 1.5h at 30 ℃ to obtain the antibacterial waterborne polyurethane;
s34, pouring antibacterial waterborne polyurethane on the surface of the leather fiber mat, and obtaining a composite material after complete permeation, wherein the use amount ratio of the leather fiber mat to the antibacterial waterborne polyurethane is 1: 3;
s4, putting the composite material into a baking oven at 50 ℃, and then acting in situ for 12 hours to obtain the antibacterial and mildewproof regenerated leather; the weight ratio of the leather fibers in the regenerated leather to the antibacterial waterborne polyurethane is 30: 70.
Example 2
A preparation method of durable antibacterial mildew-proof regenerated leather comprises the following steps:
s1, dispersing leather fibers into deionized water, and stirring to form uniform suspension;
s2, uniformly dispersing the suspension on a metal filter screen to obtain a leather fiber mat, wherein the dispersion thickness is about 1.8 mm;
s31, uniformly mixing 0.1075 parts of tetrahydrofuran homopolyether and 0.03 part of N120 in parts by weight to obtain a mixed solution;
s32, dehydrating the mixed solution at 100 ℃ for 2h, then cooling to 60 ℃, and adding 0.0200 part of neopentyl glycol; when the temperature is reduced to 40 ℃, 0.23 part of isophorone diisocyanate is added, and 0.000679 parts of dibutyltin dilaurate is added at the same time; then gradually raising the temperature to 90 ℃, and preserving the temperature for 3 hours to obtain a prepolymer;
s33, cooling the prepolymer to 40 ℃, adding a certain amount of ice water, and violently stirring to emulsify the system; thereafter, 0.000316 parts of polyhexamethylene guanidine were rapidly added, and thereafter 0.0752 part of ethylenediamine was dropwise added; finally reacting for 2 hours at 35 ℃ to obtain the antibacterial waterborne polyurethane;
s34, pouring antibacterial waterborne polyurethane on the surface of the leather fiber mat, and obtaining a composite material after complete permeation, wherein the use amount ratio of the leather fiber mat to the antibacterial waterborne polyurethane is 1: 1;
s4, putting the composite material into an oven at 70 ℃, and then performing in-situ reaction for 30 hours to obtain the antibacterial and mildewproof regenerated leather; the weight ratio of the leather fibers in the regenerated leather to the antibacterial waterborne polyurethane is 50: 50.
Example 3
A preparation method of durable antibacterial mildew-proof regenerated leather comprises the following steps:
s1, dispersing leather fibers into deionized water, and stirring to form uniform suspension;
s2, uniformly dispersing the suspension on a metal filter screen to obtain a leather fiber mat, wherein the dispersion thickness is about 2.0 mm;
s31, uniformly mixing 0.1125 parts of tetrahydrofuran homopolyether and 0.03 parts of N120 by weight to obtain a mixed solution;
s32, dehydrating the mixed solution at 100 ℃ for 2h, then cooling to 60 ℃, and adding 0.0288 parts of neopentyl glycol; when the temperature is reduced to 40 ℃, 0.27 part of isophorone diisocyanate is added, and 0.000876 parts of dibutyltin dilaurate is added at the same time; then gradually raising the temperature to 95 ℃, and preserving the temperature for 3 hours to obtain a prepolymer;
s33, cooling the prepolymer to 40 ℃, adding a certain amount of ice water, and violently stirring to emulsify the system; thereafter, 0.000438 parts of polyhexamethylene guanidine were rapidly added, and thereafter 0.080565 parts of ethylenediamine were dropwise added; finally reacting for 2.5h at 40 ℃ to obtain the antibacterial waterborne polyurethane;
s34, pouring antibacterial waterborne polyurethane on the surface of the leather fiber mat, and obtaining a composite material after complete permeation, wherein the use amount ratio of the leather fiber mat to the antibacterial waterborne polyurethane is 1: 0.4;
s4, putting the composite material into an oven at 80 ℃, and then performing in-situ reaction for 36 hours to obtain the antibacterial and mildewproof regenerated leather; the weight ratio of the leather fibers in the regenerated leather to the antibacterial waterborne polyurethane is 70: 30.
Performance testing
The performance of the recycled leather (prepared in example 2) and the leather fibers was tested, and the amount of the leather fibers was kept constant during the test.
(1) Test for chromium Release amount
The performance test was performed on the recycled leather (composite) and leather fibers (waste leather fibers).
The experimental scheme is as follows: the experiment was set up in two groups, respectively:
group 1: regenerated leather (5g regenerated leather, 40g simulated sweat)
And 2, group: leather fibre (2.5g leather fibre, 40g simulated sweat)
In the experiment, the leather fibers are kept in a certain amount, the leather fibers are respectively placed in simulated sweat with the pH values of 4, 7 and 9 for soaking for 48 hours at 37 ℃, then the solutions are respectively taken out to test the content of the Cr element in the leather fibers, the experiment result is shown in figure 2, the experiment shows that the chromium element release amount of the regenerated leather is lower than that of the leather fibers, and the chromium element release amount of the regenerated leather is lowest under a neutral condition.
Note: the simulated sweat is produced by the Chuangfeng automation technology company Limited in Dongguan city.
(2) Abrasion resistance test
The leather material and the regenerated leather (composite material) are subjected to wear resistance tests according to standard QB/T2726-.
Note: the model of the abrasion-resistant tester used in the abrasion-resistant performance test process is GT-7012-T produced by high-speed rail detection instrument Co.
(3) Resistance to mildew test
The leather material and the regenerated leather (composite material) are subjected to an anti-mildew experiment according to GB/T24346-one 2009, the test result is shown in figure 6, and the experiment result shows that: the antibacterial waterborne polyurethane disclosed by the invention takes PHMG as an antibacterial group, has a mildew-proof effect, fully considers the mildew condition possibly occurring in foot products in the daily use process, and can well resist the infection of mildew by taking the regenerated leather as a raw material of insoles.
(4) Test of antibacterial Property
The antibacterial performance test of the regenerated leather (composite material) and the waste leather fiber is carried out according to the standard GB/T20944.3-2008, the test result is shown in figure 5, and the experiment result shows that: the prepared bulk antibacterial waterborne polyurethane is fully dip-dyed with waste leather fibers by utilizing the characteristic of good fluidity, so that the stability of the material is greatly increased, and the performance of the whole material is improved; the body is antibacterial, so that the dissolution of antibacterial substances can be avoided, and the possible risks and the harm to the environment in the use process are further reduced; and the antibacterial effect is still good after the rubbing for 2500 times.
(5) Tear Strength Performance test
The method comprises the following steps of (1) carrying out tear strength test on the regenerated leather prepared in the embodiment 1-embodiment 3, cutting the composite material into a rectangular strip with the size of 4 x 1cm, then cutting an opening with the length of about two centimeters along the middle point of a short side, and finally respectively clamping the left side and the right side of the opening on an upper clamp and a lower clamp of a machine (a servo control computer system tensile testing machine with the model of AI-7000S) for testing; the test result is shown in figure 4, and the experimental result shows that the tearing strength of the regenerated leather is gradually enhanced along with the improvement of the proportion of the antibacterial waterborne polyurethane prepared by the invention.
(6) Infrared testing
The antibacterial aqueous polyurethane prepared in example 2 and the common polyurethane (self-made) were subjected to infrared test, the test results are shown in fig. 1, and when the antibacterial aqueous polyurethane prepared in the present invention was compared with the common polyurethane, the antibacterial polyurethane had a wavelength of 1645cm-1An absorption peak appears, which can be attributed to the existence of C ═ N in PHMG, while no significant absorption peak is observed in the conventional polyurethane at this position, indicating that PHMG was successfully incorporated into the polyurethane material.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (4)

1. The preparation method of the durable antibacterial mildew-proof regenerated leather is characterized by comprising the following steps:
s1, dispersing leather fibers into deionized water, and stirring to form uniform suspension;
s2, uniformly dispersing the suspension on a metal filter screen to obtain a leather fiber mat, wherein the dispersion thickness is about 1.0-2.0 mm;
s3, pouring antibacterial waterborne polyurethane on the surface of the leather fiber mat, and obtaining a composite material after complete permeation, wherein the use amount ratio of the leather fiber mat to the antibacterial waterborne polyurethane is 1: 0.4-3;
s4, putting the composite material into an oven at 50-80 ℃, and then performing in-situ action for 12-36h to obtain the antibacterial and mildewproof regenerated leather.
2. The preparation method of the durable antibacterial mildewproof regenerated leather according to claim 1, wherein the preparation method of the antibacterial waterborne polyurethane comprises the following steps of:
s31, uniformly mixing 0.075-0.1125 part of tetrahydrofuran homopolyether and 0.02-0.03 part of N120 in parts by weight to obtain a mixed solution;
s32, dehydrating the mixed solution at 100 ℃ for 2h, then cooling to 60 ℃, and adding 0.0192-0.0288 parts of neopentyl glycol; when the temperature is reduced to 40 ℃, 0.18-0.27 part of isophorone diisocyanate is added, and 0.000584-0.000876 parts of dibutyltin dilaurate are added at the same time; then gradually raising the temperature to 85-95 ℃, and preserving the temperature for 3 hours to obtain a prepolymer;
s33, cooling the prepolymer to 40 ℃, adding a certain amount of ice water, and violently stirring to emulsify the system; then 0.000292-0.000438 parts of polyhexamethylene guanidine are quickly added, and 0.05371-0.080565 parts of ethylenediamine are dropwise added; finally reacting for 1.5-2.5h at the temperature of 30-40 ℃ to obtain the antibacterial waterborne polyurethane; the polyhexamethylene guanidine is any one of polyhexamethylene biguanide hydrochloride, polyhexamethylene monoguanidine hydrochloride and polyhexamethylene guanidine phosphate.
3. The preparation method of the durable antibacterial mildewproof regenerated leather according to claim 1, which is characterized by comprising the following steps of: the weight ratio of the leather fiber in the regenerated leather to the antibacterial waterborne polyurethane is any one of 30:70, 40:60, 50:50, 60:40 and 70: 30.
4. The application of the durable antibacterial mildew-proof regenerated leather is characterized in that: the antibacterial mildewproof regenerated leather of claim 1 is used for preparing any one of shoe leather fabrics, shoe insoles and heat-insulating and heat-preserving pads.
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