CN115107322B - Environment-friendly flexible leather and preparation method thereof - Google Patents

Environment-friendly flexible leather and preparation method thereof Download PDF

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Publication number
CN115107322B
CN115107322B CN202210840767.XA CN202210840767A CN115107322B CN 115107322 B CN115107322 B CN 115107322B CN 202210840767 A CN202210840767 A CN 202210840767A CN 115107322 B CN115107322 B CN 115107322B
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flame
parts
stirring
retardant
drying
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CN115107322A (en
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李同兵
钟荣栋
刘悦
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Guangdong Antop Polymer Technology Co ltd
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Guangdong Antopu Polymer Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to environment-friendly flexible leather and a preparation method thereof, which belong to the technical field of leather preparation and comprise the following steps: soaking the base fabric in a flame-retardant polyurethane solution for treatment to obtain a flame-retardant base fabric; the following raw materials were prepared: TPU resin, lubricant, functional components, physical foaming agent, masterbatch and plasticizing auxiliary; adding the rest raw materials except the physical foaming agent into a double-screw extruder, adding the physical foaming agent into a tenth temperature zone of the double-screw extruder, foaming through a die, extruding and casting to obtain a foaming layer; pressing the flame-retardant base cloth and the foaming layer through a squeeze roller, pressing patterns, and coating a water-soluble silicone oil solution to obtain environment-friendly flexible leather; according to the invention, the base cloth is soaked by the flame-retardant polyurethane solution, the heat pressing strength between the base cloth and the foaming layer is increased while the flame retardance of the base cloth is endowed, the TPU is adopted as a base material, the foaming layer is prepared by a physical foaming technology, the environment is protected, the health is realized, and the flexibility and the flame retardance of the foaming layer are ensured by adding functional components into the foaming layer.

Description

Environment-friendly flexible leather and preparation method thereof
Technical Field
The invention belongs to the technical field of leather preparation, and particularly relates to environment-friendly flexible leather and a preparation method thereof.
Background
Thermoplastic Polyurethane (TPU) elastomer is also called thermoplastic polyurethane rubber, belongs to block polymers, consists of hard segments (isocyanate) and soft segments (polyester and polyether) which are incompatible in thermodynamics, has excellent physical and mechanical properties, has the characteristics of high elasticity, high modulus, corrosion resistance and the like, and is widely applied to synthetic leather, and TPU synthetic leather is novel environment-friendly PU synthetic leather.
Along with the improvement of the performance requirements of TPU synthetic leather in the market, particularly the requirement of flame retardant performance is outstanding, a large amount of halogen-containing organic flame retardant and inorganic flame retardant are generally added to realize the flame retardant performance of leather, the halogen-containing organic flame retardant can release toxic hydrogen halide gas in the combustion process to harm the environment and human health, and the existence of a large amount of inorganic flame retardant is difficult to uniformly disperse due to smaller particle size, so that particle aggregation is easy to generate, when leather materials are subjected to external force, stress concentration is easy to be caused at the aggregation position to cause foam in a foaming layer to break, the softness, elasticity and other performances of leather are influenced, and therefore, the flame-retardant environment-friendly flexible leather is provided based on the problem that the mechanical performance and flame retardant performance of the conventional TPU synthetic leather are difficult to combine.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides an environment-friendly flexible leather and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the environment-friendly flexible leather is obtained by hot-pressing and laminating the foaming layer and the base cloth layer, embossing textures on the foaming layer and coating the surface modification layer.
The environment-friendly flexible leather is prepared by the following steps:
the first step, soaking the base cloth in a flame-retardant polyurethane solution for 40-50min, and drying at 90-95 ℃ to obtain the flame-retardant base cloth, wherein the solid-liquid ratio of the base cloth to the flame-retardant polyurethane solution is 1g:10mL;
secondly, preparing the following raw materials in parts by weight: 100 parts of TPU resin, 0.1-0.3 part of lubricant, 2-3 parts of functional component, 2-3 parts of physical foaming agent, 1-5 parts of masterbatch and 5-10 parts of plasticizing auxiliary; adding the rest raw materials except the physical foaming agent into a double-screw extruder, adding the physical foaming agent into a tenth temperature zone of the double-screw extruder, foaming through a die, extruding and casting to obtain a foaming layer;
thirdly, pressing the flame-retardant base cloth and the foaming layer by a squeeze roller at the temperature of 95-100 ℃ and the pressure of 1.1-1.3MPa, pressing the surface patterns by a roller with surface textures at the pressure of 0.22-0.28MPa to obtain a semi-finished product, coating the surface of the semi-finished product with a water-soluble silicone oil solution at the temperature of 80-85 ℃, and drying at the temperature of 95-100 ℃ to obtain the environment-friendly flexible leather.
Further, the flame retardant polyurethane solution is prepared by the steps of:
100 parts of aqueous polyurethane emulsion, 0.3-1.2 parts of surfactant and 100-150 parts of water are stirred and mixed uniformly according to parts by weight, then 20-30 parts of composite flame retardant is added, stirring and mixing are carried out for 20-30min, a flame-retardant polyurethane solution is obtained, the solid content of the aqueous polyurethane emulsion is 25-35%, and the composite flame retardant comprises ammonium polyphosphate, diethyl aluminum hypophosphite and functional components according to the mass ratio of 1:0.5-2.0:1, wherein the surfactant is one or two of the surfactant JS-MS and the surfactant JS-BT according to any proportion.
Further, the functional component is prepared by the following steps:
step X1, uniformly mixing microcrystalline cellulose and a sulfuric acid solution with the mass fraction of 64%, stirring for 2 hours at 55 ℃, adding distilled water to stop the reaction, standing for 4-6 hours, pouring out supernatant after the reactant is precipitated, centrifugally dialyzing the residual suspension to be neutral, and freeze-drying at-45 ℃ to obtain cellulose nanocrystalline, wherein the solid-to-liquid ratio of the microcrystalline cellulose to the sulfuric acid solution is 1g:13-15mL; microcrystalline cellulose is used as a raw material, and cellulose nanocrystalline is prepared by a sulfuric acid hydrolysis method;
step X2, uniformly mixing cellulose nanocrystalline, maleic anhydride and DMF, heating to 120 ℃ under nitrogen atmosphere, stirring and reacting for 18-20h, standing for 4-6h after the reaction is finished, carrying out suction filtration, respectively washing a filter cake with absolute ethyl alcohol and deionized water for 3 times, and freeze-drying to obtain carboxylated cellulose nanocrystalline, wherein the dosage ratio of the cellulose nanocrystalline, the maleic anhydride and the DMF is 1g:8.5-10g:100-110mL, utilizing hydroxyl on the surface of the cellulose nanocrystal to carry out ring-opening esterification reaction with maleic anhydride, so as to enable the surface of the cellulose nanocrystal to be grafted with a molecular chain containing terminal carboxyl and unsaturated double bonds;
step X3, mixing carboxylated cellulose nanocrystalline, 3-chloroperoxybenzoic acid and dichloromethane, stirring and reacting for 3 hours at the temperature of 0 ℃, heating to the temperature of 40 ℃, stirring and reacting for 8-10 hours, filtering after the reaction is finished, sequentially washing a filter cake by using absolute ethyl alcohol, sodium sulfite solution with the mass fraction of 5%, sodium carbonate solution with the mass fraction of 5% and deionized water after removing dichloromethane by vacuum distillation, and freeze-drying to obtain difunctional cellulose nanocrystalline, wherein the dosage ratio of carboxylated cellulose nanocrystalline, 3-chloroperoxybenzoic acid and dichloromethane is 3.7g:1.5-1.7g:130-150mL, the surface polarity of the esterified microcrystalline cellulose is reduced, the hydrophobicity is improved, and the esterified microcrystalline cellulose is dispersed in methylene dichloride solution, so that unprotected double bonds on molecules of the esterified microcrystalline cellulose are converted into epoxy groups under the action of 3-chloroperoxybenzoic acid, and difunctional cellulose nanocrystals containing carboxyl terminal groups and epoxy groups are obtained;
step X4, mixing the difunctional cellulose nanocrystalline with DMF, adding DOPO and stirring uniformly, heating to 120 ℃ under nitrogen atmosphere, stirring and reacting for 12 hours, standing for 6-8 hours, filtering, washing a filter cake with DMF and deionized water for 3 times in sequence, and freeze-drying to obtain DOPO grafted cellulose nanocrystalline, wherein the dosage ratio of the difunctional cellulose nanocrystalline to the DMF to the DOPO is 1.5g:0.8-1.0g:40-60mL, enabling epoxy groups of the difunctional cellulose nanocrystals to react with a phosphorus-containing compound (DOPO) containing active hydrogen to enable the surfaces of the cellulose nanocrystals to be grafted with DOPO rings and generate new hydroxyl groups, so as to obtain cellulose nanocrystals containing carboxyl groups, hydroxyl groups and DOPO rings;
step X5, DOPO grafted fiberAdding the cellulose nanocrystals into DMF, dispersing uniformly, then adding an aqueous solution of ferric nitrate nonahydrate, stirring and mixing for 30min, then dripping 10% Tris solution by mass percent to adjust the pH value to 8.6, continuously stirring for 1h, standing for 4-6h, performing suction filtration, washing a filter cake with deionized water until a washing solution is neutral, and performing freeze drying to obtain a functional component; the dosage ratio of the DOPO grafted cellulose nano-crystal, DMF and ferric nitrate nonahydrate aqueous solution is 1.5g:30-40mL:10mL, aqueous solution of ferric nitrate nonahydrate, 0.6-0.7g of ferric nitrate nonahydrate and deionized water: 10mL composition, grafting carboxyl end group of cellulose nanocrystalline molecule and Fe by DOPO 3+ Forming complexation to obtain functional components.
Further, the TPU resin hardness is 60A-45D, the lubricant is a metal soap lubricant, and the plasticizing auxiliary is ACR.
Further, the temperature of the twin-screw extruder is 90-230 ℃, the die temperature is 160-190 ℃, and the physical foaming agent enters the twin-screw extruder from the exhaust port of the tenth temperature zone through the high-pressure gas cylinder.
Further, the base fabric is one of non-woven fabric, woven polyester fabric, nylon fabric and microfiber base fabric.
Further, the water-soluble silicone oil is TS-19 water-soluble silicone oil.
Further, the physical blowing agent is one of carbon dioxide, nitrogen and pentane.
The invention has the beneficial effects that:
the invention prepares polyurethane-based leather, adopts flame-retardant polyurethane solution to soak the base fabric, on one hand, endows the base fabric with flame retardance, on the other hand, increases the hot-pressing strength between the base fabric and a foaming layer, adopts TPU (thermoplastic polyurethane) as a base material, prepares the foaming layer through a physical foaming technology, does not adopt a solvent, is environment-friendly and healthy, and adds functional components instead of the existing flame retardant into the foaming layer, thereby ensuring the softness and flame retardance of the foaming layer, wherein the functional components are Fe in complex with molecules 3+ The microcrystalline cellulose which is grafted with DOPO rings on the molecules and contains a plurality of hydroxyl groups in the molecular structure is added into the TPU foaming layer to improve the strength of the foam, and the reason for improving the strength of the foam is that: multiple hydroxyl groups in the functional componentThe base is compatible with the polyurethane base material, can be uniformly distributed in the foaming material through chemical crosslinking reaction with the TPU foaming matrix, and bears a certain external force in the wall of the foam hole of the foaming material, so that the wall of the foam hole is reinforced, the structure of the foam hole is improved, and the mechanical property of the foaming material is improved; the flame retardant property is: in the combustion process of the composite material, the cellulose nanocrystalline in the functional component is Fe 3+ Is dehydrated and cracked into carbon under the catalysis of the catalyst, a compact carbon layer is formed on the surface of the composite material to prevent oxygen and heat from entering, and DOPO is pyrolyzed to generate PO 2 And PO free radical, and generates a series of aromatic hybridization structures which can further promote the formation of compact carbon layer, thereby achieving the purpose of flame retardance of condensed phase in exchange of condensed phase blocking substances and energy, PO 2 The flame-retardant polyurethane solution is also added with functional components, and the flame-retardant polyurethane solution and ammonium polyphosphate and diethyl aluminum hypophosphite cooperate to play a flame-retardant role.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a functional component, which is prepared by the following steps:
step X1, uniformly mixing 1g of microcrystalline cellulose and 13mL of 64% sulfuric acid solution, stirring at 55 ℃ for 2 hours, adding distilled water to stop the reaction, standing for 4 hours, pouring out supernatant after the reactant is precipitated, centrifugally dialyzing the residual suspension to be neutral, and freeze-drying at-45 ℃ to obtain cellulose nanocrystalline;
step X2, uniformly mixing 1g of cellulose nanocrystalline, 8.5g of maleic anhydride and 100mL of DMF, heating to 120 ℃ under nitrogen atmosphere, stirring and reacting for 18 hours, standing for 4 hours after the reaction is finished, carrying out suction filtration, respectively washing a filter cake with absolute ethyl alcohol and deionized water for 3 times, and freeze-drying to obtain carboxylated cellulose nanocrystalline;
step X3, mixing 3.7g of carboxylated cellulose nanocrystals, 1.5g of 3-chloroperoxybenzoic acid and 130mL of dichloromethane, stirring and reacting for 3 hours at 0 ℃, heating to 40 ℃, stirring and reacting for 8-10 hours, filtering after the reaction is finished, sequentially washing a filter cake by absolute ethyl alcohol, sodium sulfite solution with the mass fraction of 5%, sodium carbonate solution with the mass fraction of 5% and deionized water after removing the dichloromethane by vacuum distillation, and freeze-drying to obtain difunctional cellulose nanocrystals;
step X4, mixing 1.5g of difunctional cellulose nanocrystals with 40mL of DMF, adding 0.8g of DOPO, stirring uniformly, heating to 120 ℃ in a nitrogen atmosphere, stirring and reacting for 12 hours, standing for 6 hours, filtering, washing a filter cake with DMF and deionized water for 3 times in sequence, and freeze-drying to obtain DOPO grafted cellulose nanocrystals;
step X5, adding 1.5g DOPO grafted cellulose nanocrystalline into 30mL DMF, dispersing uniformly, then adding an aqueous solution of ferric nitrate nonahydrate, stirring and mixing for 30min, dropwise adding a 10% Tris solution by mass percent to adjust the pH value to 8.6, continuously stirring for 1h, standing for 4h, filtering, washing a filter cake with deionized water until a washing solution is neutral, and freeze-drying to obtain a functional component, wherein the aqueous solution of ferric nitrate nonahydrate is prepared from 0.6g of ferric nitrate nonahydrate and deionized water: 10 mL.
Example 2
The embodiment provides a functional component, which is prepared by the following steps:
step X1, uniformly mixing 1g of microcrystalline cellulose and 15mL of 64% sulfuric acid solution, stirring for 2 hours at 55 ℃, adding distilled water to stop the reaction, standing for 6 hours, pouring out supernatant after the reactant is precipitated, centrifugally dialyzing the residual suspension to be neutral, and freeze-drying at-45 ℃ to obtain cellulose nanocrystalline;
step X2, uniformly mixing 1g of cellulose nanocrystalline, 10g of maleic anhydride and 110mL of DMF, heating to 120 ℃ under nitrogen atmosphere, stirring and reacting for 20 hours, standing for 6 hours after the reaction is finished, carrying out suction filtration, respectively washing a filter cake with absolute ethyl alcohol and deionized water for 3 times, and freeze-drying to obtain carboxylated cellulose nanocrystalline;
step X3, mixing 3.7g of carboxylated cellulose nanocrystals, 1.7g of 3-chloroperoxybenzoic acid and 150mL of dichloromethane, stirring and reacting for 3 hours at 0 ℃, heating to 40 ℃, stirring and reacting for 10 hours, filtering after the reaction is finished, sequentially washing a filter cake by absolute ethyl alcohol, a sodium sulfite solution with the mass fraction of 5%, a sodium carbonate solution with the mass fraction of 5% and deionized water after removing dichloromethane by vacuum distillation, and freeze-drying to obtain difunctional cellulose nanocrystals;
step X4, mixing 1.5g of difunctional cellulose nanocrystals with 60mLDMF, adding 1.0g of DOPO, stirring uniformly, heating to 120 ℃ in a nitrogen atmosphere, stirring and reacting for 12 hours, standing for 8 hours, filtering, washing a filter cake with DMF and deionized water for 3 times in sequence, and freeze-drying to obtain DOPO grafted cellulose nanocrystals;
step X5, adding 1.5g DOPO grafted cellulose nanocrystalline into 40mLDMF, dispersing uniformly, then adding aqueous solution of ferric nitrate nonahydrate, stirring and mixing for 30min, dropwise adding 10% Tris solution by mass percent to adjust the pH value to 8.6, continuously stirring for 1h, standing for 6h, filtering, washing a filter cake with deionized water until a washing solution is neutral, and freeze-drying to obtain a functional component, wherein the aqueous solution of ferric nitrate nonahydrate is prepared from 0.7g of ferric nitrate nonahydrate and deionized water: 10 mL.
Example 3
The embodiment provides a flame retardant polyurethane solution which is prepared by the following steps:
100 parts of aqueous polyurethane emulsion, 0.3 part of surfactant and 100 parts of water are stirred and mixed uniformly according to parts by weight, then 20 parts of composite flame retardant is added, stirring and mixing are carried out for 20 minutes, a flame-retardant polyurethane solution is obtained, the solid content of the aqueous polyurethane emulsion is 25%, and the composite flame retardant comprises ammonium polyphosphate, diethyl aluminum hypophosphite and the functional components of the embodiment 1 according to the mass ratio of 1:0.5:1, wherein the surfactant is a surfactant JS-MS (purchased from Shanghai Crystal allied chemical Co., ltd.).
Example 4
The embodiment provides a flame retardant polyurethane solution which is prepared by the following steps:
100 parts of aqueous polyurethane emulsion, 1.2 parts of surfactant and 150 parts of water are stirred and mixed uniformly according to parts by weight, 30 parts of composite flame retardant is added, stirring and mixing are carried out for 30min, a flame-retardant polyurethane solution is obtained, the solid content of the aqueous polyurethane emulsion is 35%, and the composite flame retardant comprises ammonium polyphosphate, diethyl aluminum hypophosphite and the functional components of the embodiment 2 according to the mass ratio of 1:2.0:1, wherein the surfactant is a surfactant JS-BT (purchased from Shanghai Crystal allied chemical Co., ltd.).
Comparative example 1
The composite flame retardant in the example 3 is replaced by ammonium polyphosphate and diethyl aluminum hypophosphite according to the mass ratio of 1:0.5, and the rest of raw materials and preparation process are the same as in example 3.
Example 5
An environment-friendly flexible leather is prepared by the following steps:
the first step, soaking the base cloth in the flame-retardant polyurethane solution of the embodiment 3 for 45min, and drying at 93 ℃ to obtain the flame-retardant base cloth, wherein the solid-to-liquid ratio of the base cloth to the flame-retardant polyurethane solution is 1g:10mL;
secondly, preparing the following raw materials in parts by weight: 100 parts of TPU resin, 0.2 part of lubricant, 2 parts of functional component of example 1, 2 parts of physical foaming agent, 4 parts of color master batch and 8 parts of plasticizing auxiliary; adding the rest raw materials except the physical foaming agent into a double-screw extruder, adding the physical foaming agent into a tenth temperature zone of the double-screw extruder, foaming through a die, extruding and casting to obtain a foaming layer;
thirdly, pressing the flame-retardant base cloth and the foaming layer by a squeeze roller at the temperature of 98 ℃ and the pressure of 1.2MPa, pressing the surface patterns by a roller with surface textures at the pressure of 0.26MPa to obtain a semi-finished product, coating the surface of the semi-finished product with a water-soluble silicone oil solution at the temperature of 82 ℃, and drying at the temperature of 98 ℃ to obtain the environment-friendly flexible leather.
The TPU resin has the hardness of 67A, the lubricant is a metal soap lubricant, the plasticizing auxiliary agent is ACR, the temperature of the double-screw extruder is 90-230 ℃, the mold temperature is 180 ℃, the base cloth is woven polyester cloth, the water-soluble silicone oil is TS-19 water-soluble silicone oil, the water-soluble silicone oil is purchased from Qingdao Zhongbao silicon materials science and technology Co-Ltd, and the physical foaming agent is nitrogen.
Example 6
An environment-friendly flexible leather is prepared by the following steps:
the first step, soaking a base fabric in the flame-retardant polyurethane solution of the embodiment 4 for 40min, and drying at 90 ℃ to obtain the flame-retardant base fabric, wherein the solid-liquid ratio of the base fabric to the flame-retardant polyurethane solution is 1g:10mL;
secondly, preparing the following raw materials in parts by weight: 100 parts of TPU resin, 0.1 part of lubricant, 2 parts of functional component of example 2, 2 parts of physical foaming agent, 1 part of color master batch and 5 parts of plasticizing auxiliary; adding the rest raw materials except the physical foaming agent into a double-screw extruder, adding the physical foaming agent into a tenth temperature zone of the double-screw extruder, foaming through a die, extruding and casting to obtain a foaming layer;
thirdly, pressing the flame-retardant base cloth and the foaming layer by a squeeze roller at the temperature of 95 ℃ and the pressure of 1.1MPa, pressing the surface patterns by a roller with surface textures at the pressure of 0.22MPa to obtain a semi-finished product, coating the surface of the semi-finished product with a water-soluble silicone oil solution at 80 ℃, and drying at 95 ℃ to obtain the environment-friendly flexible leather.
The TPU resin has the hardness of 60A, the lubricant is a metal soap lubricant, the plasticizing auxiliary agent is ACR, the temperature of the double-screw extruder is 90-230 ℃, the die temperature is 160 ℃, the base fabric is non-woven fabric, the water-soluble silicone oil is TS-19 water-soluble silicone oil which is purchased from Qingdao Zhongbao silicon materials science and technology Co-Ltd, and the physical foaming agent is carbon dioxide.
Example 7
An environment-friendly flexible leather is prepared by the following steps:
the first step, soaking a base fabric in the flame-retardant polyurethane solution of the embodiment 3 for 50min, and drying at 95 ℃ to obtain the flame-retardant base fabric, wherein the solid-liquid ratio of the base fabric to the flame-retardant polyurethane solution is 1g:10mL;
secondly, preparing the following raw materials in parts by weight: 100 parts of TPU resin, 0.3 part of lubricant, 3 parts of functional component of example 2, 3 parts of physical foaming agent, 5 parts of color master batch and 10 parts of plasticizing auxiliary; adding the rest raw materials except the physical foaming agent into a double-screw extruder, adding the physical foaming agent into a tenth temperature zone of the double-screw extruder, foaming through a die, extruding and casting to obtain a foaming layer;
thirdly, pressing the flame-retardant base cloth and the foaming layer by a squeeze roller at the temperature of 100 ℃ and the pressure of 1.3MPa, pressing the surface patterns by a roller with surface textures at the pressure of 0.28MPa to obtain a semi-finished product, coating the surface of the semi-finished product with a water-soluble silicone oil solution at the temperature of 85 ℃, and drying at the temperature of 100 ℃ to obtain the environment-friendly flexible leather.
The TPU resin has the hardness of 45D as a lubricant, a metal soap lubricant, an ACR as a plasticizing auxiliary agent, a nylon cloth as a base cloth at the temperature of 90-230 ℃ and the die temperature of 190 ℃ as a die temperature, TS-19 water-soluble silicone oil as water-soluble silicone oil, and pentane as a physical foaming agent purchased from Qingdao Zhongbao silicon materials science and technology Co-Ltd.
Comparative example 2
The flame retardant polyurethane solution in example 5 was replaced with the material of comparative example 1, and the remaining raw materials and preparation process were the same as in example 5.
Comparative example 3
The functional components in the raw materials of the foaming layer in example 6 are removed, and the rest raw materials and the preparation process are the same as in example 6.
Comparative example 4
The functional components in the raw materials of the foaming layer in example 7 were removed, the flame-retardant polyurethane solution was replaced with the material of comparative example 1, and the rest of the raw materials and the preparation process were the same as in example 7.
The leathers prepared in examples 5 to 7 and comparative examples 2 to 4 were tested, tensile load was measured with reference to standard GB/T1646-2007, tear load was measured according to standard GB/T2710-2005, limiting Oxygen Index (LOI) was measured according to standard ASTMD2863-2009 using an HC-2C type oxygen index tester manufactured by Nanj Jiang Ning analytical instruments Co., ltd, and the test results are shown in Table 1:
TABLE 1
Project Tensile Strength/N Tear Strength/N Oxygen limiting index (LOI)
Example 5 606 65 29.8
Example 6 608 68 31.4
Example 7 613 70 32.9
Comparative example 2 592 63 27.6
Comparative example 3 585 61 28.4
Comparative example 4 562 58 25.2
As can be seen from Table 1, the leathers prepared in examples 5 to 7 were not only better in mechanical properties but also high in flame retardancy as compared with comparative examples 2 to 4.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (3)

1. The preparation method of the environment-friendly flexible leather is characterized by comprising the following steps of:
the first step, soaking the base cloth in a flame-retardant polyurethane solution, and drying to obtain the flame-retardant base cloth;
secondly, preparing the following raw materials in parts by weight: 100 parts of TPU resin, 0.1-0.3 part of lubricant, 2-3 parts of functional component, 2-3 parts of physical foaming agent, 1-5 parts of masterbatch and 5-10 parts of plasticizing auxiliary; adding the rest raw materials except the physical foaming agent into a double-screw extruder, adding the physical foaming agent into a tenth temperature zone of the double-screw extruder, foaming through a die, extruding and casting to obtain a foaming layer;
thirdly, pressing the flame-retardant base cloth and the foaming layer through a squeeze roller, pressing patterns to obtain a semi-finished product, coating a water-soluble silicone oil solution on the surface of the semi-finished product, and drying to obtain the environment-friendly flexible leather;
the flame-retardant polyurethane solution is prepared by the following steps:
100 parts of aqueous polyurethane emulsion, 0.3-1.2 parts of surfactant and 100-150 parts of water are stirred and mixed uniformly according to parts by weight, then 20-30 parts of composite flame retardant is added, stirring and mixing are carried out for 20-30min, and a flame-retardant polyurethane solution is obtained, wherein the composite flame retardant comprises ammonium polyphosphate, diethyl aluminum hypophosphite and functional components according to the mass ratio of 1:0.5-2.0:1, the composition is as follows;
the functional components are prepared by the following steps:
step X1, uniformly mixing microcrystalline cellulose and a sulfuric acid solution with the mass fraction of 64%, stirring for 2 hours at 55 ℃, adding distilled water to stop the reaction, standing for 4-6 hours, pouring out supernatant after the reactant is precipitated, centrifugally dialyzing the residual suspension to be neutral, and freeze-drying to obtain cellulose nanocrystalline;
step X2, uniformly mixing cellulose nanocrystals, maleic anhydride and DMF, heating to 120 ℃ under nitrogen atmosphere, stirring and reacting for 18-20h, standing for 4-6h after the reaction is finished, carrying out suction filtration, washing a filter cake, and freeze-drying to obtain carboxylated cellulose nanocrystals;
step X3, mixing carboxylated cellulose nanocrystals, 3-chloroperoxybenzoic acid and dichloromethane, stirring and reacting for 3 hours at the temperature of 0 ℃, heating to the temperature of 40 ℃, stirring and reacting for 8-10 hours, filtering after the reaction is finished, removing dichloromethane by vacuum distillation of a filter cake, washing, and freeze-drying to obtain difunctional cellulose nanocrystals;
step X4, mixing the difunctional cellulose nanocrystals with DMF, adding DOPO, stirring uniformly, heating to 120 ℃ in a nitrogen atmosphere, stirring and reacting for 12 hours, standing for 6-8 hours, filtering, washing a filter cake, and freeze-drying to obtain DOPO grafted cellulose nanocrystals;
and X5, adding DOPO grafted cellulose nanocrystals into DMF, dispersing uniformly, then adding an aqueous solution of ferric nitrate nonahydrate, stirring and mixing, dropwise adding a Tris solution to adjust the pH value to 8.6, continuously stirring for 1h, standing for 4-6h, filtering, washing a filter cake, and freeze-drying to obtain the functional component.
2. The method for preparing environment-friendly flexible leather according to claim 1, wherein the physical foaming agent is one of carbon dioxide, nitrogen and pentane.
3. An environmentally friendly flexible leather prepared by the method of any one of claims 1-2.
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