CN113512890B - Silicone rubber leather material for outdoor furniture and preparation method thereof - Google Patents

Silicone rubber leather material for outdoor furniture and preparation method thereof Download PDF

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Publication number
CN113512890B
CN113512890B CN202110845793.7A CN202110845793A CN113512890B CN 113512890 B CN113512890 B CN 113512890B CN 202110845793 A CN202110845793 A CN 202110845793A CN 113512890 B CN113512890 B CN 113512890B
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silicone rubber
parts
outdoor furniture
leather
leather material
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CN113512890A (en
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陶玉红
胥晓群
刘卫平
甘晓斌
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Guangdong Timwell Eco-Material Co ltd
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Guangdong Timwell Eco-Material Co ltd
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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
    • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10—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 by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • D06N3/106—Elastomers
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0068—Polymeric granules, particles or powder, e.g. core-shell particles, microcapsules
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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
    • 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
    • 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
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/067—Flame resistant, fire resistant
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/142—Hydrophobic
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance
    • D—TEXTILES; PAPER
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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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1692—Weather resistance
    • D—TEXTILES; PAPER
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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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/14—Furniture, upholstery
    • D—TEXTILES; PAPER
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    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • 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)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

The application relates to the field of silicone rubber leather, and particularly discloses a silicone rubber leather material for outdoor furniture and a preparation method thereof. A silicone rubber leather material for outdoor furniture comprises a base cloth and a silicone rubber material coated on the base cloth; the silicone rubber material is prepared from the following components in parts by weight: vinyl silicone rubber-based adhesive, polyvinyl silicone oil, a platinum catalyst, a silane coupling agent, an inhibitor and a hydrophobic auxiliary agent; the hydrophobic auxiliary agent comprises the following components in parts by weight: 5.5-10 parts of hollow silicon dioxide, 1.5-3 parts of methyltrimethoxysilane, 1-2 parts of hydroxyl-terminated polydimethylsiloxane, 1-1.5 parts of 2-ethyl-4-methylimidazole, 0.5-1 part of long-acting antibacterial biological carbon material and 2-5 parts of epoxy resin. The silicone rubber leather material for outdoor furniture has the advantages of good hydrophobic property, strong friction resistance, lasting antibacterial property and excellent heat aging resistance.

Description

Silicone rubber leather material for outdoor furniture and preparation method thereof
Technical Field
The application relates to the field of silicone rubber leather, in particular to a silicone rubber leather material for outdoor furniture and a preparation method thereof.
Background
The synthetic leather is an artificial leather which has appearance and hand feeling similar to real leather and can replace the real leather, and is widely applied in life, and comprises various fields such as clothes, gloves, bags, furniture, vamps and the like.
In the prior art, chinese patent application No. CN202011163312.6 discloses a processing technology of PU synthetic leather, wherein, the PU resin uses polyol and isocyanate as synthetic raw materials, dimethyl formamide and diphenylmethane diisocyanate as solvents, and toner, deodorant and anti-fouling agent are added and stirred to prepare the PU resin, and after the base cloth is ironed, the PU resin slurry is coated on the base cloth.
The PU resin uses polyalcohol and isocyanate as pigments and is matched with a plurality of auxiliary agents, but the isocyanate is mainly TDI or MDI, and because the main chain formed by combining the isocyanate and hydroxyl has strong polarity, the PU synthetic leather is easy to decompose in a humid environment or water, so that the water resistance of the PU synthetic leather is poor.
In order to improve the problems, the chinese patent application with application number CN201410576901.5 discloses a novel waterproof synthetic leather slurry and a preparation method thereof, wherein the slurry comprises the following raw materials in parts by weight: 110-120 parts of waterborne polyurethane resin, 10-12 parts of trimellitic anhydride, 0.4-0.5 part of methyl tetrahydrophthalic anhydride, 1.5-1.6 parts of sodium dodecyl sulfate, 1-2 parts of vegetable gum, 0.5-0.8 part of smoked sheet, 43-45 parts of barium sulfate powder, 6-8 parts of peanut leaf, 3.5-4.5 parts of silane coupling agent G-570 and 25-30 parts of tetrahydrofuran.
Aiming at the related technologies, the inventor thinks that the waterproof synthetic leather has a good waterproof effect, but because the hydrophobicity is poor, water drops remain on the surface of the leather for a long time after the leather is wetted, and when the waterproof synthetic leather is used for outdoor furniture, bacteria are bred or mildewed on the surface of the leather due to the fact that rainwater easily carries the bacteria, and the performance of the leather is affected.
Disclosure of Invention
In order to improve the hydrophobicity of the leather for outdoor furniture and prevent rainwater from being remained on the outdoor furniture for a long time to cause bacteria or mildew on the surface of the leather, the application provides a silicone rubber leather material for the outdoor furniture and a preparation method thereof.
In a first aspect, the application provides a silicone rubber leather material for outdoor furniture, which adopts the following technical scheme:
a silicone rubber leather material for outdoor furniture comprises a base cloth and a silicone rubber material coated on the base cloth;
the silicone rubber material is prepared from the following components in parts by weight: 10-20 parts of vinyl silicone rubber-based adhesive, 0.5-1 part of polyvinyl silicone oil, 0.01-0.05 part of platinum catalyst, 0.5-1.5 parts of silane coupling agent, 0.01-0.05 part of inhibitor and 1-5 parts of hydrophobic auxiliary agent;
the hydrophobic auxiliary agent comprises the following components in parts by weight: 5.5-10 parts of hollow silicon dioxide, 1.5-3 parts of methyltrimethoxysilane, 1-2 parts of hydroxyl-terminated polydimethylsiloxane, 1-1.5 parts of polyamide, 0.5-1 part of long-acting antibacterial biological carbon material and 2-5 parts of epoxy resin.
By adopting the technical scheme, the silicone rubber leather material is prepared by adopting the components such as the vinyl silicone rubber base material, the polyvinyl silicone oil and the like, the main chain of the organic silicon is Si-O-Si, and no double bond exists, so the organic silicon is not easy to be decomposed by ultraviolet rays and ozone, meanwhile, the chain length of the Si-O bond is about 1.5 times of that of the C-C bond, and the chain length is longer, so that the organic silicon has better thermal stability and weather resistance than other high polymer materials, the service life of the organic silicon in a natural environment can reach up to years, and the intermolecular force of the organic silicon is weaker than that of a hydrocarbon, so the organic silicon leather material has lower viscosity, lower surface tension and lower surface energy than that of a hydrocarbon with the same molecular weight, has better water resistance and hydrophobicity, and is doped with a hydrophobic assistant prepared by the components such as hollow silicon dioxide, methyltrimethoxysilane, hydroxyl-terminated polydimethylsiloxane, epoxy resin and the like, so the hydrophobic effect of the leather material can be further improved.
The long-acting antibacterial biological carbon material in the hydrophobic auxiliary agent is a quaternized biological carbon antibacterial powder, has very good amphipathy and dispersibility, has high-efficiency, spectral and lasting antibacterial activity, and good thermal stability, the particle size of the hollow silica is nano-scale to micro-scale, and has the characteristics of large specific surface area, low density, good stability and the like, but the surface of the hollow silica has hydrophilicity, and the methyltrimethoxysilane can modify the surface of the hollow silica to form a non-polar organic film containing methyl on the surface of the hollow silica, so that the hollow silica has a super-hydrophobic effect; and the network generated by the silicon dioxide and the hydroxyl-terminated polydimethylsiloxane is tighter due to the action of hydrogen bonds, the hydroxyl groups outside and inside the hollow silicon dioxide aggregate are replaced, and the hydrophobicity of the silicon dioxide is further improved.
The modified silicon dioxide is used as a compatibilizer of epoxy resin and hydroxyl-terminated polydimethylsiloxane, the epoxy resin has the performances of excellent cohesiveness, low curing shrinkage rate and the like, but is crisp in quality, poor in impact resistance effect and easy to crack, the hydroxyl-terminated polydimethylsiloxane is used for modifying the epoxy resin, a flexible Si-O chain can be introduced into a cured structure of the epoxy resin, the internal stress of the epoxy resin can be reduced, the fracture toughness and heat resistance of the epoxy resin can be improved, the surface tension of the epoxy resin is reduced, the hydrophobicity is improved, and in addition, the hydroxyl-terminated polydimethylsiloxane can play a double role in protecting hollow silicon dioxide particles and reducing the surface energy of leather, so that the leather still has a hydrophobic effect after being rubbed for many times.
Preferably, the hydrophobic auxiliary agent is prepared by the following method:
(1) Mixing methyltrimethoxysilane with methanol and oxalic acid solution, stirring for 30-40min, hydrolyzing at room temperature for 10-12h, adding hollow silica and ammonia water, stirring for 20-24h, centrifuging and washing to obtain surface-modified hollow silica, wherein the mass ratio of the methanol and oxalic acid solution to the methyltrimethoxysilane is (0.9-1);
(2) Dissolving surface-modified hollow silica and hydroxyl-terminated polydimethylsiloxane in absolute ethyl alcohol, and performing ultrasonic dispersion to prepare a mixed solution, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the surface-modified hollow silica to the absolute ethyl alcohol is 1.5-1;
(3) Uniformly dispersing epoxy resin, polyamide, a long-acting antibacterial biological carbon material and a mixed solution, and drying in vacuum at 65-70 ℃ to prepare a hydrophobic auxiliary agent, wherein the mass ratio of the mixed solution to the epoxy resin is 0.8-1.2.
By adopting the technical scheme, firstly, the surface of the hollow silicon dioxide is modified by methyl trimethoxy silane, amino groups are grafted on the surface of the hollow silicon dioxide to form an organic membrane containing methyl, so that the surface of the hollow silicon dioxide is nonpolar, the hydrophobic effect is improved, meanwhile, the compatibility of the hollow silicon dioxide and hydroxyl-terminated polydimethylsiloxane is increased, the hollow silicon dioxide is uniformly infiltrated and dispersed in the hydroxyl-terminated polydimethylsiloxane, the hydroxyl of the modified hollow silicon dioxide is substituted under the action of the hydroxyl-terminated polydimethylsiloxane, and the hydrophobicity is further improved; epoxy groups on the surface of the hollow silicon dioxide participate in the curing reaction of the epoxy resin to improve the compatibility of the epoxy resin with the epoxy resin, and hydroxyl groups on the surface of the hollow silicon dioxide have hydrogen bond action with the hydroxyl-terminated polydimethylsiloxane to enable the hydroxyl-terminated polydimethylsiloxane to be a compatibilizer of the epoxy resin and the hydroxyl-terminated polydimethylsiloxane, so that the hydroxyl-terminated polydimethylsiloxane and the epoxy resin form an interpenetrating network, and the flexibility, the tensile strength and the thermal stability of the epoxy resin are improved.
Preferably, in the step (1), the hollow silica is calcined at 500-550 ℃ for 5-6h before being mixed with methyltrimethoxysilane, and then boiled in boiling water for 1.5-2h.
By adopting the technical scheme, the hollow silicon dioxide is calcined and boiled, and then the hydroxyl on the surface of the hollow silicon dioxide is reactivated, so that the hollow silicon dioxide is convenient to be grafted with the amino in the methyltrimethoxysilane.
Preferably, in the step (3), before vacuum drying, tetramethylammonium polyhedral oligomeric silsesquioxane and graphene are added, and after uniform dispersion, vacuum drying is performed at 65-70 ℃ to obtain the hydrophobic assistant, wherein the mass ratio of the tetramethylammonium polyhedral oligomeric silsesquioxane to the graphene to the epoxy resin is 0.6-1-0.2.
By adopting the technical scheme, the fiber diameter of the tetramethylammonium polyhedral oligomeric silsesquioxane is 0.5-2 microns, the tetramethylammonium polyhedral oligomeric silsesquioxane is an inorganic core consisting of silicon-oxygen frameworks which are alternately connected by Si-O, has good compatibility with epoxy resin, has the advantages of light weight, high toughness, wear resistance, corrosion resistance and the like, can improve the mechanical property and the heat-resistant temperature of the epoxy resin, increases the durability of the hydrophobic effect of leather, and prevents the hydrophobic effect of the leather from weakening after multiple times of friction; the graphene has lower shearing force and friction coefficient, is easy to transfer to a leather material to form a transfer film on the surface of the leather material, and improves the wear resistance of the leather material.
Preferably, the graphene is pretreated by the following steps: acidifying graphene, adding a KH-560 absolute ethanol solution with the mass fraction of 2-3%, ultrasonically dispersing, carrying out constant-temperature water bath at 60-70 ℃ for 5-6h, carrying out vacuum filtration, washing until the pH value is 7, and carrying out vacuum drying, wherein the mass ratio of the graphene to the KH-560 ethanol solution is 1.
By adopting the technical scheme, the graphene has hydroxyl and carboxyl, and is difficult to disperse uniformly with epoxy resin, after acidification, active functional groups appear on the surface of the graphene, so that a coupling agent KH560 is convenient to graft, and a silane coupling agent KH-560 is subjected to hydrolysis and condensation with acidified graphene carboxyl, so that the graphene is uniformly dispersed in the epoxy resin, on one hand, the toughness of the epoxy resin is improved, on the other hand, the bonding strength between the graphene and the epoxy resin is improved, and therefore, the wear-resistant effect of the leather material is improved.
Preferably, the inhibitor is one or a combination of several of methylbutynol, ethynylcyclohexanol and 3,7, 11-trimethyldodecyn-3-ol;
the concentration of the platinum catalyst is 5000ppm, and the platinum catalyst is ethanol, isopropanol, vinyl silicone oil and dimethyl silicone oil solution; the platinum catalyst is one of chloroplatinic acid isopropanol solution and chloroplatinic acid-1, 3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl-cyclotetrasiloxane; the Pt atom content in the platinum catalyst is 1000-10000ppm;
the silane coupling agent is one or a mixture of more than two of KH-560, KH-570, methyl triethoxysilane and methyl orthosilicate.
Preferably, a repair material is further arranged between the base cloth and the silicon rubber material, and the repair material comprises the following components in parts by weight: 0.8-1.5 parts of tea tree oil, 0.3-0.8 part of nano-silver, 0.3-0.5 part of citric acid, 2-4 parts of water, 0.8-1.2 parts of aqueous polyurethane emulsion, 0.09-0.11 part of sucrose ester and 1-2 parts of carboxymethyl chitosan.
By adopting the technical scheme, because the leather for outdoor furniture is in an outdoor environment for a long time, the leather is easy to crack, harden, become brittle and the like after being irradiated by the sun, the sucrose ester is used as an emulsifier, the carboxymethyl chitosan is used as a wall material, the tea tree oil and the nano silver are used as core materials, and the waterborne polyurethane is used as a binder to form a repairing material which contains microcapsules and has an adhesion effect, the repairing material is adhered between base cloth and a silicon rubber material, the carboxymethyl chitosan has degradability, and the carboxymethyl chitosan used as the wall material is continuously degraded in the outdoor environment, the tea tree oil and the nano silver in the repairing material are continuously released, so that the wettability and the antibacterial durability of the leather material are improved, and the continuously released tea tree oil can prevent the leather material from hardening, becoming brittle and even cracking at high temperature.
Preferably, the repair material is prepared by the following method: mixing citric acid and water, heating to 50-60 ℃, adding carboxymethyl chitosan, sucrose ester, nano silver and tea tree oil, uniformly mixing, spray-drying under the conditions that the spray pressure is 380-420KPa, the air inlet temperature is 180-185 ℃, and the air outlet temperature is 90-100 ℃, and uniformly mixing the product obtained by spray-drying and the waterborne polyurethane emulsion.
By adopting the technical scheme, citric acid is firstly dissolved in water to prepare a citric acid solution, carboxymethyl chitosan is dissolved in the citric acid solution, then sucrose ester, nano-silver and tea tree oil are added, after uniform emulsification, spray drying is carried out, the carboxymethyl chitosan is coated on the surfaces of the tea tree oil and the nano-silver, and then the carboxymethyl chitosan is mixed with the aqueous polyurethane emulsion to form the repairing material with adhesiveness.
In a second aspect, the application provides a preparation method of a silicone rubber leather material for outdoor furniture, which adopts the following technical scheme:
a preparation method of a silicone rubber leather material for outdoor furniture comprises the following steps:
preparation of a silicone rubber material: dispersing and uniformly stirring vinyl silicone rubber-based glue, polyvinyl silicone oil, a platinum catalyst, a silane coupling agent, an inhibitor and a hydrophobic auxiliary agent;
preparation of silicone rubber leather: coating a silicon rubber material on release paper, attaching the release paper to base cloth, pressing, vulcanizing at 100-140 ℃, and stripping the release paper to obtain the silicon rubber leather material for outdoor furniture.
By adopting the technical scheme, the silicone rubber material is attached to the base cloth by the release paper, and the leather material is prepared by pressing and vulcanizing, so that the preparation method is simple, and the industrial production is easy to realize.
Preferably, before the base cloth is attached to the silicone rubber material, one side of the base cloth is coated with a repair material, after the base cloth is cured, the side with the repair material is attached to the silicone rubber material, and the repair material comprises the following components in parts by weight: 0.8-1.5 parts of tea tree oil, 0.3-0.8 part of nano-silver, 0.3-0.5 part of citric acid, 2-4 parts of water, 0.8-1.2 parts of aqueous polyurethane emulsion, 0.09-0.11 part of sucrose ester and 1-2 parts of carboxymethyl chitosan.
By adopting the technical scheme, the repair material positioned between the base cloth and the silicon rubber material can be adhered to the base cloth and is bonded with the silicon rubber material after being cured, and the nano silver and the tea tree oil with the antibacterial effect are released in the continuous degradation process of the carboxymethyl chitosan, so that the wettability of the leather material is increased, the leather material is prevented from hardening and cracking due to high temperature, and the heat-resistant aging performance of the leather material is improved.
In summary, the present application has the following beneficial effects:
1. the silicone rubber leather is prepared from the vinyl silicone rubber-based rubber, the polyvinyl silicone oil and the like, and the chain length of the Si-O bond is longer than that of the C-C bond, so that the silicone has better thermal stability and weather resistance, and the acting force between silicone molecules is weaker, so that the silicone has lower surface tension and surface energy, and therefore the silicone rubber leather has better hydrophobicity.
2. According to the application, the hydrophobic auxiliary agent is preferably prepared by adopting hollow silicon dioxide, methyltrimethoxysilane and the like, and the methyltrimethoxysilane forms a non-polar organic film on the surface of the hollow silicon dioxide, so that the hollow silicon dioxide has a super-hydrophobic effect, and in addition, under the compatibilization effect of the hollow silicon dioxide, the hydroxyl-terminated polydimethylsiloxane and the epoxy resin form an interpenetrating network, so that the fracture toughness, the heat resistance and the hydrophobic effect of the epoxy resin are improved; in addition, under the action of hydroxyl-terminated polydimethylsiloxane, the leather surface still has a high hydrophobic effect after being rubbed for many times.
3. According to the application, the tetramethyl ammonium cage-shaped polysilsesquioxane and the graphene are preferably doped into the hydrophobic auxiliary agent, the two have the advantages of high toughness, good abrasive performance and corrosion resistance, the tetramethyl ammonium cage-shaped polysilsesquioxane and the epoxy resin are good in compatibility, and the tear strength and the wear resistance of the leather material can be improved after the tetramethyl ammonium cage-shaped polysilsesquioxane and the epoxy resin are blended.
4. In the application, the repairing material is preferably coated between the base cloth and the silicon rubber material, the repairing material is composed of microcapsules and waterborne polyurethane, wherein the microcapsules and the waterborne polyurethane are made of carboxymethyl chitosan coated tea tree oil and nano silver, and the tea tree oil and the nano silver with antibacterial effects are continuously released along with the degradation of the carboxymethyl chitosan, so that the antibacterial durability of the leather material is prolonged, the tea tree oil can increase the internal wettability of the leather material, the conditions of dry cracking, hardening, embrittlement and the like on the surface of the leather material after the leather material is exposed to high temperature are prevented, and the heat-resistant aging performance of the leather material is improved.
Detailed Description
Preparation examples 1 to 9 of hydrophobic auxiliary
The epoxy resin in preparation examples 1-9 is selected from Kyoto Kailada energy science and technology, inc. of Guangzhou, model No. E51; the polyamide is selected from Zhang Jia gang Yarui chemical Co., ltd, and the model is V140; the hollow silica is selected from Sian Ruixi biological technology, inc. with the model of R-ZK18005; the methyltrimethoxysilane is selected from Nanjing Quanxi chemical company, inc., with a product number of 6070; the hydroxyl-terminated polydimethylsiloxane is selected from Conditis chemical industry (Hubei) Co.Ltd, and the mark is AA; the long-acting antibacterial biological carbon material is selected from Zhengzhou Ookang biological material Co., ltd, with the model of Acps; the tetramethyl ammonium polyhedral oligomeric silsesquioxane is selected from Hubei Xin Rundji, and has a CAS number of 69866-29-4; the graphene is selected from Dongguan pure technical materials Limited, and the model is SM; KH-560 is selected from the Chang Yi Xin plastication Ming Hu of Dongguan city, having a product number of 410221.
Preparation example 1: (1) Placing hollow silica with the particle size of 180nm at 500 ℃ for calcining for 6h, then placing in boiling water for boiling for 1.5h, mixing 1.5kg of methyltrimethoxysilane with 1.35kg of methanol and 0.45kg of oxalic acid solution with the concentration of 0.01moL/L, stirring for 30min, hydrolyzing at room temperature for 10h, adding 5.5kg of hollow silica and 1.1kg of ammonia water, stirring for 20h, centrifuging, washing for 2 times by using absolute ethyl alcohol to prepare the surface-modified hollow silica, wherein the mass ratio of the methanol, the oxalic acid solution and the methyltrimethoxysilane is 0.9;
(2) Dissolving 0.5kg of surface-modified hollow silica and 1kg of hydroxyl-terminated polydimethylsiloxane in 3kg of absolute ethanol, and performing ultrasonic dispersion to prepare a mixed solution, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the surface-modified hollow silica to the absolute ethanol is 1.5;
(3) Uniformly dispersing 2kg of epoxy resin, 1kg of polyamide, 0.5kg of long-acting antibacterial biochar material and 1.6kg of mixed solution, and drying at 65 ℃ in vacuum to prepare a hydrophobic auxiliary agent, wherein the mass ratio of the mixed solution to the epoxy resin is 0.8.
Preparation example 2: (1) Placing hollow silica with the particle size of 200nm at 530 ℃ for calcining for 5.5h, then placing in boiling water for boiling for 1.8h, mixing 2.5kg of methyltrimethoxysilane with 2.5kg of methanol and 1kg of oxalic acid solution with the concentration of 0.01moL/L, stirring for 35min, hydrolyzing at room temperature for 11h, adding 8.5kg of hollow silica and 2.55kg of ammonia water, stirring for 22h, centrifuging, washing for 2 times by using absolute ethyl alcohol to prepare the surface-modified hollow silica, wherein the mass ratio of the methanol, the oxalic acid solution and the methyltrimethoxysilane is 1;
(2) Dissolving 1.2kg of surface-modified hollow silica and 1.5kg of hydroxyl-terminated polydimethylsiloxane in 3kg of absolute ethanol, and performing ultrasonic dispersion to prepare a mixed solution, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the surface-modified hollow silica to the absolute ethanol is 1.8;
(3) Uniformly dispersing 4kg of epoxy resin, 1.3kg of polyamide, 0.8kg of long-acting antibacterial biochar material and 4kg of mixed solution, and drying in vacuum at 65 ℃ to prepare the hydrophobic auxiliary agent, wherein the mass ratio of the mixed solution to the epoxy resin is 1.
Preparation example 3: (1) Placing hollow silica with the particle size of 200nm at 550 ℃ for calcining for 5h, then placing the hollow silica in boiling water for boiling for 2h, mixing 3kg of methyltrimethoxysilane with 3kg of methanol and 1.5kg of oxalic acid solution with the concentration of 0.01moL/L, stirring for 40min, hydrolyzing at room temperature for 12h, adding 10kg of hollow silica and 4kg of ammonia water, stirring for 24h, centrifuging, washing with absolute ethyl alcohol for 2 times, and preparing the surface-modified hollow silica, wherein the mass ratio of the methanol to the oxalic acid solution to the methyltrimethoxysilane is 1;
(2) Dissolving 2kg of surface-modified hollow silica and 2kg of hydroxyl-terminated polydimethylsiloxane in 3kg of absolute ethanol, and performing ultrasonic dispersion to prepare a mixed solution, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the surface-modified hollow silica to the absolute ethanol is 1;
(3) Uniformly dispersing 5kg of epoxy resin, 1.5kg of polyamide, 1kg of long-acting antibacterial biochar material and 6kg of mixed solution, and drying in vacuum at 70 ℃ to prepare the hydrophobic auxiliary agent, wherein the mass ratio of the mixed solution to the epoxy resin is 1.2.
Preparation example 4: the difference from preparation example 1 is that, in step (3), 1.2kg of tetramethylammonium polyhedral oligomeric silsesquioxane and 0.4kg of graphene are added before vacuum drying, and are uniformly dispersed with 2kg of epoxy resin, 1kg of polyamide and 1.6kg of mixed solution and vacuum dried at 65 ℃, and the mass ratio of the tetramethylammonium polyhedral oligomeric silsesquioxane to the graphene to the epoxy resin is 0.6.
Preparation example 5: the difference from preparation example 1 is that, in step (3), 1.6kg of tetramethylammonium polyhedral oligomeric silsesquioxane and 0.6kg of graphene are added before vacuum drying, and are uniformly dispersed in 2kg of epoxy resin, 1kg of polyamide and 1.6kg of mixed solution and vacuum dried at 70 ℃, and the mass ratio of tetramethylammonium polyhedral oligomeric silsesquioxane to graphene to epoxy resin is 0.8.
Preparation example 6: the difference from preparation example 1 is that, in step (3), 2kg of tetramethylammonium polyhedral oligomeric silsesquioxane and 0.5kg of graphene are added before vacuum drying, and the mixture is uniformly dispersed with 2kg of epoxy resin, 1kg of polyamide and 1.6kg of mixed solution and vacuum dried at 70 ℃, wherein the mass ratio of the tetramethylammonium polyhedral oligomeric silsesquioxane to the graphene to the epoxy resin is 1.
Preparation example 7: the difference from preparation example 4 is that graphene is pretreated as follows: acidifying graphene, adding a KH-560 absolute ethanol solution with the mass fraction of 2%, ultrasonically dispersing for 1h, carrying out constant-temperature water bath at 60 ℃ for 6h, carrying out vacuum filtration, washing with ethanol until the pH is 7, and carrying out vacuum drying at 80 ℃, wherein the mass ratio of the graphene to the KH-560 ethanol solution is 1.
Preparation example 8: the graphene is pretreated by the following steps: acidifying graphene, adding a KH-560 absolute ethanol solution with the mass fraction of 3%, ultrasonically dispersing for 1h, carrying out constant-temperature water bath at 70 ℃ for 5h, carrying out vacuum filtration, washing with ethanol until the pH is 7, and carrying out vacuum drying at 80 ℃, wherein the mass ratio of the graphene to the KH-560 ethanol solution is 1.
Preparation example 9: the graphene is pretreated by the following steps: acidifying graphene, adding a KH-560 absolute ethanol solution with the mass fraction of 3%, ultrasonically dispersing for 1h, carrying out constant-temperature water bath at 65 ℃ for 6h, carrying out vacuum filtration, washing with ethanol until the pH is 7, and carrying out vacuum drying at 80 ℃, wherein the mass ratio of the graphene to the KH-560 ethanol solution is 1.
Preparation examples 1 to 6 of repair materials
The carboxymethyl chitosan in preparation examples 1 to 6 was selected from Cimanan Hengji chemical Co., ltd, model number HJ; the NANO silver is selected from Guangzhou Pokung chemical engineering and technology Limited, and the product number is NANO-AG-P; the tea tree oil is selected from Hongsheng spice oil Co., ltd, jian, and has a product number of A-002; the waterborne polyurethane emulsion is selected from Shenzhen Jitian chemical Co., ltd, with the model number of F0400; the citric acid is selected from Suzhou Huafeng chemical industry Co., ltd, with the product number of SH-74.
Preparation example 1: mixing 0.3kg of citric acid and 2kg of water, heating to 50 ℃, adding 1kg of carboxymethyl chitosan, 0.09kg of sucrose ester, 0.3kg of nano silver and 0.8kg of tea tree oil, uniformly mixing, spray-drying under the conditions that the spray pressure is 380KPa, the air inlet temperature is 180 ℃ and the air outlet temperature is 90 ℃, and uniformly mixing the product obtained by spray-drying and 0.8kg of aqueous polyurethane emulsion.
Preparation example 2: mixing 0.4kg of citric acid and 3kg of water, heating to 60 ℃, adding 1.5kg of carboxymethyl chitosan, 0.1kg of sucrose ester, 0.5kg of nano silver and 1.1kg of tea tree oil, uniformly mixing, spray-drying under the conditions that the spray pressure is 400KPa, the air inlet temperature is 185 ℃ and the air outlet temperature is 95 ℃, and uniformly mixing the product obtained by spray-drying and 1kg of aqueous polyurethane emulsion.
Preparation example 3: mixing 0.5kg of citric acid and 4kg of water, heating to 55 ℃, adding 2kg of carboxymethyl chitosan, 0.11kg of sucrose ester, 0.8kg of nano silver and 1.2kg of tea tree oil, uniformly mixing, spray-drying under the conditions that the spray pressure is 420KPa, the air inlet temperature is 185 ℃ and the air outlet temperature is 100 ℃, and uniformly mixing the product obtained by spray-drying and 1.2kg of aqueous polyurethane emulsion.
Preparation example 4: 0.3kg of citric acid, 2kg of water, 1kg of carboxymethyl chitosan, 0.09kg of sucrose ester, 0.3kg of nano-silver, 0.8kg of tea tree oil and 0.8kg of aqueous polyurethane emulsion are mixed uniformly.
Preparation example 5: the difference from preparation example 1 is that tea tree oil was not added.
Preparation example 6: the difference from preparation example 1 is that nano silver is not added.
Examples
In the following embodiments, the nano antibacterial non-woven fabric is selected from the limited technology of precision measurement and control of the Foshan California, 110-2S is selected from the limited technology of Shenzhen Mu, 110-3S is selected from the limited technology of Shenzhen Mu, the vinyl silicone oil with the viscosity of 10000cs is selected from the limited silicon fluoride material of Shenzhen Jipeng, and the product number is 002; the vinyl silicone oil with viscosity of 20000cs is selected from blue silicone rubber antibacterial company Limited in Dongguan city and is of the brand LG-T20000; KH-560 and KH-570 are selected from Shandong bright commercial chemical Co., ltd; the CAS number for chloroplatinic acid-1, 3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl-cyclotetrasiloxane is 27342-69-4; the methylbutinol is selected from south-Tong-Zongzhun New chemical Co., jiangsu province; ethynyl cyclohexanol is selected from chemical raw materials ltd, located in great longevity, guangzhou; CAS number for 3,7, 11-trimethyldodecyn-3-ol is 160-35-9.
Example 1: a silicone rubber leather material for outdoor furniture comprises a base cloth and a silicone rubber material coated on the base cloth, wherein the base cloth is a nano antibacterial non-woven fabric, the bacteriostatic rate of the nano antibacterial non-woven fabric on escherichia coli, staphylococcus aureus and candida albicans reaches more than 99%, the raw material proportion of the silicone rubber material is shown in table 1, the vinyl content of vinyl silicone rubber base rubber in table 1 is 0.13-0.20%, and the type is 110-2S; the viscosity of the vinyl silicone oil is 10000cs, the inhibitor is methyl butynol, the platinum catalyst is chloroplatinic acid isopropanol solution, the Pt atom content in the platinum catalyst is 1000ppm, and the silane coupling agent is KH-560 and KH-570 in the mass ratio of 1.
The preparation method of the silicone rubber leather material for outdoor furniture comprises the following steps:
s1, preparation of a silicon rubber material: adding vinyl silicone rubber-based glue, polyvinyl silicone oil, a platinum catalyst, a silane coupling agent, an inhibitor and a hydrophobic auxiliary agent into a planetary dispersion stirrer, introducing cooling water, and dispersing and stirring for 10min;
s2, preparing the silicone rubber leather: coating a silicon rubber material on release paper, attaching the release paper to a base fabric, pressing for 5s under 0.5MPa, vulcanizing at 100 ℃ for 10min to obtain a silicon rubber layer, and stripping the release paper to obtain the silicon rubber leather material for outdoor furniture, wherein the thickness of the silicon rubber layer is 0.2mm.
TABLE 1 raw material ratios of silicone rubber materials in examples 1-13
Figure BDA0003180497820000091
Examples 2 to 5: a silicone rubber leather material for outdoor furniture, which is different from example 1 in the amount of raw materials of the silicone rubber material, and is specifically shown in table 1.
Examples 6 to 13: a silicone rubber leather material for outdoor furniture, which is different from the material in example 1 in that the source of the hydrophobic auxiliary agent is different, and is specifically shown in table 1.
Example 14: a silicone rubber leather material usable for outdoor furniture, differing from example 13 in that a vinyl silicone rubber base rubber has a vinyl content of 0.21 to 0.24% and a type of 110 to 3S, the vinyl silicone oil has a viscosity of 20000cs, an inhibitor is ethynylcyclohexanol and 3,7, 11-trimethyldodecyn-3-ol in a mass ratio of 1.
Example 15: a silicone rubber leather material usable for outdoor furniture, which is different from example 13 in that a repair material is further coated between a base fabric and a silicone rubber material, the repair material being made from preparation example 1 of the repair material.
The preparation method of the silicone rubber leather material for outdoor furniture comprises the following steps:
s1, preparation of a silicon rubber material: adding vinyl silicone rubber-based glue, polyvinyl silicone oil, a platinum catalyst, a silane coupling agent, an inhibitor and a hydrophobic auxiliary agent into a planetary dispersion stirrer, introducing cooling water, and dispersing and stirring for 10min;
s2, preparing the silicone rubber leather: coating a repairing material on one side of a base fabric, drying for 120s at 80 ℃ to form a repairing layer, wherein the thickness of the repairing layer is 0.05mm, coating a silicon rubber material on release paper, attaching the silicon rubber material to one side of the base fabric with the repairing material, pressing for 5s at 0.5MPa, vulcanizing for 10min at 100 ℃ to obtain a silicon rubber layer, and stripping the release paper to obtain the silicon rubber leather material for outdoor furniture, wherein the thickness of the silicon rubber layer is 0.1mm.
Example 16: a silicone rubber leather material usable for outdoor furniture, differing from example 15 in that the repair material was made of preparation example 2 of the repair material, and the thickness of the repair layer was 0.1m.
Example 17: a silicone rubber leather material usable for outdoor furniture, differing from example 15 in that the repair material was made of preparation example 3 of the repair material, and the thickness of the repair layer was 0.15m.
Example 18: a silicone rubber leather material usable for outdoor furniture, which is different from example 15 in that a repair material was made from preparation example 4 of the repair material.
Example 19: a silicone rubber leather material usable for outdoor furniture, which is different from example 15 in that a repair material was made from preparation example 5 of the repair material.
Example 20: a silicone rubber leather material usable for outdoor furniture, which is different from example 15 in that a repair material was made from preparation example 6 of the repair material.
Comparative example
Comparative example 1: a silicone rubber leather material useful for outdoor furniture, which is different from example 1 in that hollow silica is not added to the hydrophobic auxiliary agent.
Comparative example 2: a silicone rubber leather material for outdoor furniture, which is different from the material in example 1 in that no hydroxy-terminated polydimethylsiloxane is added to the hydrophobic auxiliary agent.
Comparative example 3: a silicone rubber leather material which can be used for outdoor furniture, and is different from the silicone rubber leather material in example 1 in that methyltrimethoxysilane is not added into a hydrophobic auxiliary agent.
Comparative example 4: a silicone rubber leather material for outdoor furniture, which is different from the example 1 in that a long-acting antibacterial biochar material is not added in a hydrophobic auxiliary agent.
Comparative example 5: the preparation method of the environment-friendly outdoor sofa leather sequentially comprises the following steps: the base cloth is prepared by coating water-soluble polyvinyl alcohol on the base cloth at 100 deg.C, and oven drying at 110 deg.C. 0.8 weight part of rubber elastomer TPR, 0.2 weight part of silicone oil and 1 weight part of environment-friendly color master batch are heated by an extruder to 160 ℃ for melt mixing, and then the mixture is compounded with the prepared base cloth under the pressure of 0.5MPa through a die head and release paper with veins to prepare the preliminary outdoor special sofa leather. And (3) strengthening the preliminary outdoor special sofa leather in water with the temperature of 35 ℃, and drying to prepare the full-environment-friendly outdoor special sofa leather.
Comparative example 6: a hydrophobic adjuvant is selected from Australian chemical industry Co., ltd, dongguan, with model number of SD-BPS217.
Performance test
Leather materials were prepared according to the methods in examples and comparative examples, and the properties of the leather materials were measured according to the following methods, and the results of the measurements are reported in Table 2.
1. Contact angle: placing the leather fabric on a video optical contact angle measuring instrument to measure the static contact angle of the leather surface, adopting 5 mu L water drops to test, testing 5 different positions of each leather fabric, and taking the average value of the positions as the final test result; fixing the leather material at an inclination angle of 45 degrees, impacting 50g of sand grains with the diameter of 300-1000um on the leather surface inclined at 45 degrees from the height of 40cm, impacting different times and recording the change of the static contact angle of the leather.
2. The bacteriostasis rate is as follows: samples of the same specification were taken, left outdoors for 4 weeks, and then examined according to ASTM E-2149-01, "determination of antibacterial behavior of steady-state antibacterial agent under dynamic contact conditions".
3. Tear strength: the detection is carried out according to QB/T1646-2007 polyurethane synthetic leather.
4. Resistance to wet heat aging: according to QB/T4448-2013 'determination of peel strength of hard facing materials on furniture surfaces', the specification of a sample is 15mm multiplied by 200mm, 20 identical samples are tested in each example or comparative example, 5 samples in each example or comparative example are firstly peeled off 50mm from a silicon rubber layer and a base fabric in the length direction, the peeled parts cannot be obviously damaged, the speed of a stretching machine is 30-40mm/min, the temperature is 23 +/-2 ℃ and the relative humidity is 50 +/-2%, the initial peel strength is tested, and the average value of 5 samples is taken; the samples of examples or comparative examples were subjected to a constant temperature and humidity test at a temperature of 70 ℃ for 3 weeks, 4 weeks and 5 weeks, and 5 samples were placed for each example or comparative example for measurement, and the measurement results were averaged.
TABLE 2 Performance test results of leather materials
Figure BDA0003180497820000111
Figure BDA0003180497820000121
In examples 1 to 5, the hydrophobic auxiliary prepared in preparation example 1 using the hydrophobic auxiliary is added to the raw materials for preparing leather materials, the prepared leather materials have a static contact angle of (159.2 to 160.3) ° and a bacteriostatic rate of more than 95%, and have a good hydrophobic effect and a durable antibacterial effect, and the leather materials prepared in examples 1 to 5 have a high tear strength, a radial tear strength of (52 to 55) N/30mm, a latitudinal tear strength of (42 to 45) N/30mm, and an initial peel strength of (15.23 to 15.41) N/15mm, and after aging for 5 weeks at 70 ℃ and 90 rh, the peel strength still reaches (13.02 to 13.07) N/15mm, and have good thermal aging resistance.
Examples 6 and 7 the hydrophobic auxiliary agents obtained in preparation examples 2 and 3 using the hydrophobic auxiliary agent, respectively, and it is shown from the data in table 2 that the leather materials prepared in examples 6 to 7 have initial contact angles similar to those of example 1, and have excellent mechanical properties and thermal aging resistance.
In examples 8 to 10, the hydrophobic assistant prepared in preparation examples 4 to 6 using the hydrophobic assistant was added with tetramethylammonium cage polysilsesquioxane and graphene, as compared with example 1, it can be seen from the comparison of the data that the leather material prepared in examples 8 to 10 had an initial contact angle increased as compared with example 1, but after 10 times of sand rubbing, the contact angle was (157.9 to 158.6) ° and after 20 times of rubbing, the contact angle was (151.4 to 151.9) ° and was significantly increased as compared with example 1, and in addition, the bacteriostatic rate of the leather material was increased, which indicates that tetramethylammonium cage polysilsesquioxane and graphene increased the friction resistance of the leather material, extended the hydrophobic durability of the leather material, and improved the initial hydrophobic effect and antimicrobial durability of the leather material.
The hydrophobic auxiliary agents prepared in preparation examples 7 to 9 using the hydrophobic auxiliary agents in examples 11 to 13 have insignificant difference between the initial contact angle and the contact angle after rubbing of the leather materials prepared in examples 11 to 13 compared with example 8, but the radial tear strength is increased to (58 to 59) N/30mm, and the latitudinal tear strength is increased to (47 to 49) N/30mm, which shows that the mechanical properties of the leather materials can be improved after the graphene is treated by acidification and a coupling agent.
In example 14, the raw material of the silicone rubber material was different and the thickness of the silicone rubber layer was different from that of example 1, and the tear strength of the leather material prepared in example 14 was increased from that of example 1 as compared with example 1.
The difference between examples 15-17 and example 13 is that the base fabric and the silicone rubber layer were further coated with a repair material, and the repair material was prepared from preparation examples 1-3 of the repair material, and it can be seen from the comparison of the data in table 2 that the contact angle of the leather material was not greatly changed before and after rubbing in examples 15-17, but the bacteriostatic ratio of the leather material was significantly increased to (99.5-99.8)%, and the peel strength was increased, and the peel strength was (14.83-14.98) N/15mm after being left at 70 ℃ for 3 weeks, the peel strength was (14.31-14.36) N/15mm after being left for 4 weeks, and the peel strength was (13.78-13.87) N/15mm after being left for 5 weeks, compared with example 13, the heat aging resistance was improved.
Example 18 compared with example 15, the repair material was prepared by directly mixing citric acid, water, carboxymethyl chitosan, sucrose ester, nano silver, tea tree oil and aqueous polyurethane emulsion, and the leather material prepared in comparative example 5 had a hydrophobic property, an antibacterial property and a mechanical property which were not much different from those of example 15, but had a remarkably decreased peel strength and a decreased heat aging resistance after aging at 70 ℃ for 3 weeks.
Example 19 compared to example 15, the repair material was not added with tea tree oil, and the leather material prepared in example 19 had hydrophobic effect and mechanical properties similar to those of example 15, but its lasting antibacterial effect was decreased and heat aging resistance was also decreased.
Compared with the example 15, the repair material of the example 20 is not added with the nano silver, and the leather material prepared by the example 20 has little difference in hydrophobic effect, mechanical property and thermal aging resistance compared with the example 15, but the antibacterial lasting property is reduced.
Compared with example 1, the hydrophobic assistant is not added with hollow silica, and as can be seen from the data in table 2, the initial contact angle of the leather material prepared in comparative example 1 is 145.7 °, and the contact angle is reduced after coarse sand friction, which indicates that the hollow silica can enhance the hydrophobicity and the wear resistance of the leather material, so that the leather material still maintains the superhydrophobic performance after sand impact friction.
Compared with the example 1, the hydrophobic auxiliary agent is not added with the hydroxyl-terminated polydimethylsiloxane, the contact angle of the comparative example 2 is similar to that of the example 1, but the tear strength is reduced, and the peel strength is weakened after aging for 3 weeks at 70 ℃, so that the hydroxyl-terminated polydimethylsiloxane can improve the mechanical property and the heat-resistant effect of the leather material.
Comparative example 3 compared to example 1, the leather material prepared in comparative example 3 had a decreased initial contact angle without much deterioration of the remaining properties due to the addition of methyltrimethoxysilane to the hydrophobic adjuvant.
Compared with the example 1, the long-acting antibacterial biological carbon material is not added in the hydrophobic auxiliary agent, the contact angle of the leather material prepared in the comparative example 4 with water is large, the leather material still keeps the hydrophobic effect after sand impact friction, and in addition, the heat aging resistance is good, but the antibacterial effect is reduced.
Comparative example 5 is a leather material prepared by the method in the prior art, which has a poor hydrophobic effect, weak antibacterial durability, and poor thermal aging resistance, although having good mechanical properties.
Comparative example 6 is a commercially available hydrophobic aid, and the contact angle is high, reaching 159.4 °, and after sand impact friction, the contact angle is significantly reduced, the superhydrophobic property is difficult to maintain continuously, the heat aging resistance effect is poor, and the antibacterial durability is insufficient.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. The silicone rubber leather material for outdoor furniture is characterized by comprising base cloth and a silicone rubber material coated on the base cloth;
the silicone rubber material is prepared from the following components in parts by weight: 10-20 parts of vinyl silicone rubber-based adhesive, 0.5-1 part of polyvinyl silicone oil, 0.01-0.05 part of platinum catalyst, 0.5-1.5 parts of silane coupling agent, 0.01-0.05 part of inhibitor and 1-5 parts of hydrophobic auxiliary agent;
the hydrophobic auxiliary agent comprises the following components in parts by weight: 5.5-10 parts of hollow silicon dioxide, 1.5-3 parts of methyltrimethoxysilane, 1-2 parts of hydroxyl-terminated polydimethylsiloxane, 1-1.5 parts of polyamide, 0.5-1 part of long-acting antibacterial biological carbon material and 2-5 parts of epoxy resin;
the hydrophobic auxiliary agent is prepared by the following method:
(1) Mixing methyltrimethoxysilane with methanol and oxalic acid solution, stirring for 30-40min, hydrolyzing at room temperature for 10-12h, adding hollow silica and ammonia water, stirring for 20-24h, centrifuging and washing to obtain surface-modified hollow silica, wherein the mass ratio of the methanol and oxalic acid solution to the methyltrimethoxysilane is 0.9-1;
(2) Dissolving surface-modified hollow silica and hydroxyl-terminated polydimethylsiloxane in absolute ethyl alcohol, and performing ultrasonic dispersion to prepare a mixed solution, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the surface-modified hollow silica to the absolute ethyl alcohol is (1);
(3) Uniformly dispersing epoxy resin, polyamide, a long-acting antibacterial biological carbon material and a mixed solution, adding tetramethyl ammonium group cage-shaped polysilsesquioxane and graphene, uniformly dispersing, and drying in vacuum at 65-70 ℃ to prepare a hydrophobic auxiliary agent, wherein the mass ratio of the mixed solution to the epoxy resin is 0.8-1.2.
2. The silicone rubber leather material for outdoor furniture according to claim 1, wherein in step (1), the hollow silica is calcined at 500-550 ℃ for 5-6 hours before being mixed with methyltrimethoxysilane, and then boiled in boiling water for 1.5-2 hours.
3. The silicone rubber leather material usable for outdoor furniture according to claim 1, characterized in that the graphene is pretreated by: acidifying graphene, adding a KH-560 absolute ethanol solution with the mass fraction of 2-3%, ultrasonically dispersing, carrying out constant-temperature water bath at 60-70 ℃ for 5-6h, carrying out vacuum filtration, washing until the pH value is 7, and carrying out vacuum drying, wherein the mass ratio of the graphene to the KH-560 ethanol solution is 1.
4. The silicone rubber leather material applicable to outdoor furniture according to claim 1, characterized in that the inhibitor is one or a combination of several of methylbutynol, ethynylcyclohexanol, 3,7, 11-trimethyldodecyn-3-ol;
the platinum catalyst is one of chloroplatinic acid isopropanol solution and chloroplatinic acid-1, 3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl-cyclotetrasiloxane; the Pt atom content in the platinum catalyst is 1000-10000ppm;
the silane coupling agent is one or a mixture of more than two of KH-560, KH-570, methyl triethoxysilane and methyl orthosilicate.
5. The silicone rubber leather material for outdoor furniture according to claim 1, wherein a repair material is further arranged between the base cloth and the silicone rubber material, and the repair material comprises the following components in parts by weight: 0.8-1.5 parts of tea tree oil, 0.3-0.8 part of nano-silver, 0.3-0.5 part of citric acid, 2-4 parts of water, 0.8-1.2 parts of aqueous polyurethane emulsion, 0.09-0.11 part of sucrose ester and 1-2 parts of carboxymethyl chitosan.
6. The silicone rubber leather material usable for outdoor furniture according to claim 5, characterized in that the repair material is produced by: mixing citric acid and water, heating to 50-60 ℃, adding carboxymethyl chitosan, sucrose ester, nano silver and tea tree oil, uniformly mixing, spray-drying under the conditions that the spray pressure is 380-420KPa, the air inlet temperature is 180-185 ℃, and the air outlet temperature is 90-100 ℃, and uniformly mixing the product obtained by spray-drying and the waterborne polyurethane emulsion.
7. The method for preparing the silicone rubber leather material usable for outdoor furniture according to any one of claims 1 to 4, characterized by comprising the steps of:
preparation of a silicone rubber material: dispersing and uniformly stirring vinyl silicone rubber-based glue, polyvinyl silicone oil, a platinum catalyst, a silane coupling agent, an inhibitor and a hydrophobic auxiliary agent;
preparation of silicone rubber leather: coating a silicon rubber material on release paper, attaching the release paper to base cloth, pressing, vulcanizing at 100-140 ℃, and stripping the release paper to obtain the silicon rubber leather material for outdoor furniture.
8. The preparation method of the silicone rubber leather material for outdoor furniture according to claim 7, wherein before the base cloth is attached to the silicone rubber material, one side of the base cloth is coated with the repair material, and after the base cloth is cured, the side with the repair material is attached to the silicone rubber material, and the repair material comprises the following components in parts by weight: 0.8-1.5 parts of tea tree oil, 0.3-0.8 part of nano-silver, 0.3-0.5 part of citric acid, 2-4 parts of water, 0.8-1.2 parts of aqueous polyurethane emulsion, 0.09-0.11 part of sucrose ester and 1-2 parts of carboxymethyl chitosan.
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