阅读说明：本技术 一种船舶、游艇家具装饰用有机硅合成革及其制备方法 (Organic silicon synthetic leather for furniture decoration of ships and yachts and preparation method thereof ) 是由 陶玉红 胥晓群 刘卫平 甘晓斌 于 2021-09-08 设计创作，主要内容包括：本申请涉及合成革领域,具体公开了一种船舶、游艇家具装饰用有机硅合成革及其制备方法。船舶、游艇家具装饰用有机硅合成革包括基层和涂覆在基层上的合成革浆料；合成革浆料包括以下组分：3-5份苯基乙烯基硅树脂、10-12份乙烯基硅油、1-3份乙烯基氟硅油、1-2份含氢硅油、0.3-0.5份硅烷偶联剂、0.01-0.03份阻聚剂、0.05-0.1份铂金催化剂、2-6份低温增韧剂；低温增韧剂包括以下组分：3-5份环氧树脂、1-2份聚芳醚酮、1.5-3份纳米勃姆石粉、5-8份超高分子量聚乙烯。本申请的船舶、游艇家具装饰用有机硅合成革具有低温下弯曲性能好,且疏水、透气,防海水腐蚀,与基层粘结强度高的优点。(The application relates to the field of synthetic leather, and particularly discloses organic silicon synthetic leather for furniture decoration of ships and yachts and a preparation method thereof. The organic silicon synthetic leather for decorating the furniture of the ships and yachts comprises a base layer and synthetic leather slurry coated on the base layer; the synthetic leather slurry comprises the following components: 3-5 parts of styrene-vinyl silicone resin, 10-12 parts of vinyl silicone oil, 1-3 parts of vinyl fluorosilicone oil, 1-2 parts of hydrogen-containing silicone oil, 0.3-0.5 part of silane coupling agent, 0.01-0.03 part of polymerization inhibitor, 0.05-0.1 part of platinum catalyst and 2-6 parts of low-temperature toughening agent; the low-temperature toughening agent comprises the following components: 3-5 parts of epoxy resin, 1-2 parts of polyaryletherketone, 1.5-3 parts of nano boehmite powder and 5-8 parts of ultrahigh molecular weight polyethylene. The organic silicon synthetic leather for decoration of ships and yachts has the advantages of good bending performance at low temperature, hydrophobicity, breathability, seawater corrosion resistance and high bonding strength with a base layer.)

1. The organic silicon synthetic leather for furniture decoration of ships and yachts is characterized by comprising a base layer and synthetic leather slurry coated on the base layer;

the synthetic leather slurry comprises the following components in parts by weight: 3-5 parts of styrene-vinyl silicone resin, 10-12 parts of vinyl silicone oil, 1-3 parts of vinyl fluorosilicone oil, 1-2 parts of hydrogen-containing silicone oil, 0.3-0.5 part of silane coupling agent, 0.01-0.03 part of polymerization inhibitor, 0.05-0.1 part of platinum catalyst and 2-6 parts of low-temperature toughening agent;

the low-temperature toughening agent comprises the following components in parts by weight: 3-5 parts of epoxy resin, 1-2 parts of polyaryletherketone, 1.5-3 parts of nano boehmite powder and 5-8 parts of ultrahigh molecular weight polyethylene.

2. The organic silicon synthetic leather for ship and yacht furniture decoration according to claim 1, wherein: the low-temperature toughening agent is prepared by the following method: (1) dissolving ultrahigh molecular weight polyethylene in decalin, adding nano boehmite powder, mixing uniformly, and spinning to prepare ultrahigh molecular weight polyethylene fiber;

(2) mixing and melting epoxy resin and polyaryletherketone, soaking the ultrahigh molecular weight polyethylene fiber prepared in the step (1) in the melted mixture of epoxy resin and polyaryletherketone, solidifying and crushing to prepare the low-temperature toughening agent.

3. The organic silicon synthetic leather for ship and yacht furniture decoration according to claim 2, wherein: the ultrahigh molecular weight polyethylene fiber and the epoxy resin in the step (1) are pretreated by the following steps before impregnation: soaking the ultra-high molecular weight polyethylene fiber in an acid solution at the temperature of 40-80 ℃, and then drying at the temperature of 100-130 ℃, wherein the mass ratio of the ultra-high molecular weight polyethylene fiber to the acid solution is 1: 3-5.

4. The organic silicon synthetic leather for ship and yacht furniture decoration according to claim 3, wherein: the acid solution consists of the following components in percentage by weight: 10-50% of sulfuric acid, 40-70% of potassium permanganate and 10-20% of 2-ammonium acrylate.

5. The organic silicon synthetic leather for ship and yacht furniture decoration according to claim 1, wherein: the synthetic leather slurry also comprises 2-5 parts by weight of preservative, wherein the preservative is prepared by mixing, extruding and granulating EVA, sea-island fiber, collagen fiber and organic modified montmorillonite, and the mass ratio of the EVA, the sea-island fiber, the collagen fiber and the organic modified montmorillonite is 1:0.1-0.5:0.3-0.7: 0.2-0.5.

6. The organic silicon synthetic leather for decorating ship and yacht furniture according to claim 5, wherein the organic modified montmorillonite is prepared by the following method:

(1) adding 0.5-1 part by weight of montmorillonite into 8-10 parts by weight of ethanol solution, performing ultrasonic dispersion uniformly, adding 1.5-2 parts by weight of ammonia water with the mass concentration of 15-25% and 3-4 parts by weight of ethyl orthosilicate, reacting for 20-24h, performing suction filtration, performing ultrasonic dispersion in distilled water, repeating suction filtration and ultrasonic dispersion in distilled water for 3-5 times, and drying at 50-60 ℃ to obtain an intermediate;

(2) mixing 0.5-1 weight part of intermediate with 3-5 weight parts of absolute ethyl alcohol, 4-5 weight parts of ammonia water and 4-8 weight parts of vinyl triethoxysilane, stirring uniformly at 30-40 ℃, centrifuging, washing for 3-5 times with absolute ethyl alcohol, and drying at 50-60 ℃.

7. The silicone synthetic leather for decorating ship and yacht furniture according to claim 1, wherein the base layer is high-strength glass fiber cloth.

8. The organic silicon synthetic leather for decorating ship and yacht furniture according to claim 7, wherein the high-strength glass fiber cloth is pretreated by the following steps: soaking the high-strength glass fiber cloth in a hydrogen peroxide solution with the concentration of 25-30%, taking out, cleaning with distilled water, drying, spraying a silane coupling agent, and drying, wherein the spraying amount of the silane coupling agent is 20-30% of the mass of the high-strength glass fiber cloth.

9. The organic silicon synthetic leather for decorating ship and yacht furniture according to claim 8, wherein the high-strength glass fiber cloth is further coated with an adhesive layer formed by curing an adhesive, the adhesive layer is positioned between the base layer and the synthetic leather slurry, and the adhesive comprises the following components in parts by weight: 8-10 parts of silicon rubber-based adhesive, 0.5-1 part of hydrogen-containing silicone oil, 0.1-0.3 part of tackifier, 0.01-0.05 part of platinum catalyst and 0.02-0.1 part of polymerization inhibitor;

the preparation method of the tackifier comprises the following steps: mixing 1-3 parts by weight of phenolic resin and 0.4-0.6 part by weight of graphene oxide, reacting at 70-80 ℃ for 2-3h to obtain a graphene oxide modified phenolic resin solution, cooling to 30-40 ℃, adding 0.8-1.2 parts by weight of urea and 0.4-0.5 part by weight of melamine, uniformly mixing at 55-60 ℃, cooling to room temperature, adding 0.1-0.3kg of ammonium sulfate, and uniformly stirring to obtain the tackifier.

10. A preparation method of organic silicon synthetic leather for decoration of furniture of ships and yachts is characterized by comprising the following steps:

preparing synthetic leather slurry: uniformly kneading phenyl vinyl silicone resin, vinyl silicone oil, vinyl fluorosilicone oil, hydrogen-containing silicone oil, a silane coupling agent, a polymerization inhibitor, a platinum catalyst and a low-temperature toughening agent to prepare synthetic leather slurry;

manufacturing of synthetic leather: and coating the synthetic leather slurry on release paper, then compounding the release paper with the base layer, vulcanizing, and stripping the release paper to prepare the synthetic leather.

Technical Field

The application relates to the technical field of synthetic leather, in particular to organic silicon synthetic leather for furniture decoration of ships and yachts and a preparation method thereof.

Background

Synthetic leather is a composite material which simulates the tissue structure and the service performance of natural leather and can be used as a substitute of the natural leather, and is widely applied to the fields of producing bags, clothes, automotive interiors and the like. The polyurethane synthetic leather is a simulated leather synthetic leather which takes various cloth bases as base materials and is coated with polyurethane resin to endow various patterns, functions and handfeel on the base materials.

Yachts and ships are waterborne vehicles integrating navigation, sports, entertainment and leisure, and a large amount of synthetic leather is used for decoration in the yachts and ships.

In the prior art, chinese patent application with application number CN201911362755.5 discloses an outdoor leather for yachts and a preparation method thereof, the outdoor leather for yachts comprises a base fabric layer, a wet-process PU bottom layer, a dry-process PU surface layer and a surface treatment layer, which are sequentially arranged, the dry-process PU surface layer comprises a first dry-process PU surface layer, a second dry-process PU surface layer and a third dry-process PU surface layer, which are sequentially formed between the wet-process PU bottom layer and the surface treatment layer, the first dry-process PU surface layer is located between the second dry-process PU surface layer and the surface treatment layer, the third dry-process PU surface layer is located between the wet-process PU bottom layer and the second dry-process PU surface layer, the wet-process PU bottom layer is a flame-retardant PU layer, and the first dry-process PU surface layer is a PU mildew-proof layer.

The leather for the yacht has the performances of corrosion resistance, ultraviolet resistance, hydrolysis resistance, mildew resistance, bacteria resistance and the like, and has better aging resistance than PVC material yacht leather, but because sea breeze is larger and the air temperature is lower at seaside and in winter, the synthetic leather for decoration on the yacht is harder at low temperature and is easy to break and crack.

Disclosure of Invention

In order to improve the low-temperature toughness of synthetic leather for yachts and ships, the application provides organic silicon synthetic leather for furniture decoration of ships and yachts and a preparation method thereof.

First aspect, this application provides a boats and ships, yacht furniture are decorated and are used organosilicon synthetic leather, adopts following technical scheme:

an organic silicon synthetic leather for decorating furniture of ships and yachts comprises a base layer and synthetic leather slurry coated on the base layer;

the synthetic leather slurry comprises the following components in parts by weight: 3-5 parts of styrene-vinyl silicone resin, 10-12 parts of vinyl silicone oil, 1-3 parts of vinyl fluorosilicone oil, 1-2 parts of hydrogen-containing silicone oil, 0.3-0.5 part of silane coupling agent, 0.01-0.03 part of polymerization inhibitor, 0.05-0.1 part of platinum catalyst and 2-6 parts of low-temperature toughening agent;

the low-temperature toughening agent comprises the following components in parts by weight: 3-5 parts of epoxy resin, 1-2 parts of polyaryletherketone, 1.5-3 parts of nano boehmite powder and 5-8 parts of ultrahigh molecular weight polyethylene.

By adopting the technical scheme, the synthetic leather slurry is prepared from the phenyl vinyl silicone resin, the vinyl silicone oil and the like, and the prepared synthetic leather has the advantages of low surface energy, yellowing resistance, good aging resistance and good thermal stability; the epoxy resin, the polyaryletherketone, the nano boehmite powder and the ultra-high molecular weight polyethylene are used as components of the low-temperature flexibilizer, the epoxy resin belongs to thermosetting resin and has good low-temperature resistance effect, the lowest applicable temperature is about-50 ℃, the polyaryletherketone belongs to thermoplastic resin and can effectively absorb fracture energy at low temperature when being mixed with the epoxy resin, the nano boehmite powder can also form a microstructure for absorbing the fracture energy in the epoxy resin, and when the nano boehmite powder and the polyether aryl ketone are matched for use, the nano boehmite powder can form a complex microstructure between the epoxy resin and the polyaryletherketone, so that the interface energy absorption structure is more and more effective, the crack propagation resistance is improved, and the low-temperature toughness of the synthetic leather is improved; the ultra-high molecular weight polyethylene has excellent low-temperature mechanical properties, can keep excellent impact strength even in liquid nitrogen, has better corrosion resistance and weather resistance, can further enhance the low-temperature toughness of the synthetic leather, and prevents the synthetic leather from becoming brittle, cracking and the like at low temperature when used on yachts and ship furniture.

Preferably, the low-temperature toughening agent is prepared by the following method: (1) dissolving ultrahigh molecular weight polyethylene in decalin, adding nano boehmite powder, mixing uniformly, and spinning to prepare ultrahigh molecular weight polyethylene fiber;

(2) mixing and melting epoxy resin and polyaryletherketone, soaking the ultrahigh molecular weight polyethylene fiber prepared in the step (1) in the melted mixture of epoxy resin and polyaryletherketone, solidifying and crushing to prepare the low-temperature toughening agent.

By adopting the technical scheme, the nano boehmite powder is white flowable hydrated alumina powder which has the characteristic of easy dispersion, is mixed with the decahydronaphthalene solution of the ultra-high molecular weight polyethylene and can be uniformly dispersed in the decahydronaphthalene solution of the ultra-high molecular weight polyethylene solution, the ultra-high molecular weight polyethylene fiber is prepared after spinning, and then the ultra-high molecular weight polyethylene fiber is soaked in the melted mixture of the epoxy resin and the polyaryletherketone, so that the phenomenon that the nano boehmite powder is not uniformly dispersed due to poor interface compatibility in the mixture of the epoxy resin and the polyaryletherketone can be prevented, strong van der Waals force exists between the nano boehmite powder and an organic silicon material and is dispersed in the organic silicon synthetic leather slurry, the stress concentration phenomenon of a defect position at low temperature can be effectively improved, energy can be transmitted, cracks of the organic silicon synthetic leather are prevented from being blocked, and passivated, and further the organic silicon synthetic leather is prevented from developing destructive cracks, and the nano boehmite powder has a good specific surface area, so that the surface of the ultra-high molecular weight polyethylene fiber prepared by spinning has high porosity, thereby promoting the full infiltration of the epoxy resin and the polyaryletherketone on the surface, and ensuring that the coating amount of the epoxy resin and the polyaryletherketone is high and the toughness is strong.

Preferably, in the step (1), the ultrahigh molecular weight polyethylene fiber is pretreated with the epoxy resin and before impregnation as follows: soaking the ultra-high molecular weight polyethylene fiber in an acid solution at the temperature of 40-80 ℃, and then drying at the temperature of 100-130 ℃, wherein the mass ratio of the ultra-high molecular weight polyethylene fiber to the acid solution is 1: 3-5.

By adopting the technical scheme, the ultrahigh molecular weight polyethylene fiber is subjected to surface treatment by using an acidic solution, so that oxygen-containing functional groups such as hydroxyl, carboxyl and the like are introduced into the surface of the ultrahigh molecular weight polyethylene fiber, the surface activity of the ultrahigh molecular weight polyethylene fiber is enhanced, fine and uniform pits appear on the surface of the ultrahigh molecular weight polyethylene fiber, and the functional groups are connected to the surface of the ultrahigh molecular weight polyethylene fiber in a covalent bond mode, so that the compatibility of the surface of the ultrahigh molecular weight polyethylene fiber with epoxy resin and polyaryletherketone is greatly improved, and the low temperature resistance of the synthetic leather is further improved.

Preferably, the acid solution consists of the following components in percentage by weight: 10-50% of sulfuric acid, 40-70% of potassium permanganate and 10-20% of 2-ammonium acrylate.

By adopting the technical scheme, the acid solution prepared by the method has oxygen-containing functional groups, can endow the surface of the ultra-high molecular weight polyethylene fiber with higher surface activity, and improves the compatibility of the surface of the ultra-high molecular weight polyethylene fiber with epoxy resin and polyaryletherketone.

Preferably, the synthetic leather slurry also comprises 2-5 parts by weight of preservative, wherein the preservative is prepared by mixing, extruding and granulating EVA, sea-island fiber, collagen fiber and organic modified montmorillonite, and the mass ratio of the EVA, the sea-island fiber, the collagen fiber and the organic modified montmorillonite is 1:0.1-0.5:0.3-0.7: 0.2-0.5.

By adopting the technical scheme, because the seawater has higher salt content and contains more microorganisms, the seawater can cause corrosion or mildew in the synthetic leather after entering the synthetic leather through permeation; therefore, the mildew inhibitor prepared from EVA, sea-island fibers, collagen fibers and organic modified montmorillonite is added into the composite material, the sea-island fibers have the advantages of large specific surface area and good covering property and fluffiness, and also have remarkable waterproofness, air permeability and high adsorbability, the bending rigidity is small, the collagen fibers have certain elasticity, the flexibility of the organic silicon synthetic leather can be improved, the wear resistance is improved, the surface energy of the EVA is low, the contact angle with water is large, the hydrophobicity is good, the composite material has barrier property to oxygen and water vapor, and the organic modified montmorillonite has hydrophobic and breathable effects after being modified by organic matters.

Because EVA has excellent barrier property, the air permeability of the synthetic leather is weakened, and sea-island fibers and collagen fibers are doped into the EVA to form a three-dimensional cross-linked network in the EVA, so that the EVA has the functions of a framework and a support, and forms a structure similar to dermal collagen fibers and is distributed on the surface of the synthetic leather, so that the air permeability of the synthetic leather is increased, but the three-dimensional cross-linked structure has smaller pores and is difficult to pass water; the organic modified montmorillonite enhances the air permeability of the EVA, so that the synthetic leather with good air permeability, high hydrophobicity and low water permeability is formed, seawater is prevented from wetting on the surface of the synthetic leather or permeating into the synthetic leather, and the synthetic leather is prevented from being corroded or mildewed.

The EVA and the collagen fibers have strong low-temperature resistance, so that the synthetic leather is not easy to embrittle at low temperature, and the low-temperature resistance of the synthetic leather can be further improved; the organic modified montmorillonite can improve the adhesion between EVA and polar polymer, thereby improving the binding force between the synthetic leather slurry and the preservative.

Preferably, the organically modified montmorillonite is prepared by the following method:

(1) adding 0.5-1 part by weight of montmorillonite into 8-10 parts by weight of ethanol solution, performing ultrasonic dispersion uniformly, adding 1.5-2 parts by weight of ammonia water with the mass concentration of 15-25% and 3-4 parts by weight of ethyl orthosilicate, reacting for 20-24h, performing suction filtration, performing ultrasonic dispersion in distilled water, repeating suction filtration and ultrasonic dispersion in distilled water for 3-5 times, and drying at 50-60 ℃ to obtain an intermediate;

(2) mixing 0.5-1 weight part of intermediate with 3-5 weight parts of absolute ethyl alcohol, 4-5 weight parts of ammonia water and 4-8 weight parts of vinyl triethoxysilane, stirring uniformly at 30-40 ℃, centrifuging, washing for 3-5 times with absolute ethyl alcohol, and drying at 50-60 ℃.

By adopting the technical scheme, the silicon dioxide is coated on the surface of the montmorillonite to prepare the silicon dioxide coated montmorillonite intermediate, and then the silicon dioxide coated montmorillonite is subjected to surface modification by adopting the vinyltriethoxysilane, so that the hydrophobicity of the surface of the silicon dioxide is improved, the super-hydrophobic modified montmorillonite with excellent acid and alkali resistance, weather resistance and durability is prepared, the surface hydrophobicity of the synthetic leather is improved, and seawater is prevented from permeating into the synthetic leather.

Preferably, the base layer is high-strength glass fiber cloth.

By adopting the technical scheme, the high-strength glass fiber cloth has good high-low temperature resistance, strong aging resistance, difficult shrinkage and deformation and good flame retardance.

Preferably, the high-strength glass fiber cloth is pretreated by the following steps: soaking the high-strength glass fiber cloth in a hydrogen peroxide solution with the concentration of 25-30%, taking out, cleaning with distilled water, drying, spraying a silane coupling agent, and drying, wherein the spraying amount of the silane coupling agent is 20-30% of the mass of the high-strength glass fiber cloth.

By adopting the technical scheme, the affinity between the high-strength glass fiber cloth and the synthetic leather slurry is poor, so that the interface bonding strength is not high, the high-strength glass fiber cloth is subjected to acid etching by using a hydrogen peroxide solution, and then the silane coupling agent grafting is carried out, so that the affinity between the high-strength glass fiber cloth and the synthetic leather slurry is enhanced, and the bonding strength is increased.

Preferably, the high-strength glass fiber cloth is further coated with an adhesive layer formed by curing an adhesive, the adhesive layer is positioned between the base layer and the synthetic leather slurry, and the adhesive comprises the following components in parts by weight: 8-10 parts of silicon rubber-based adhesive, 0.5-1 part of hydrogen-containing silicone oil, 0.1-0.3 part of tackifier, 0.01-0.05 part of platinum catalyst and 0.02-0.1 part of polymerization inhibitor;

the preparation method of the tackifier comprises the following steps: mixing 1-3 parts by weight of phenolic resin and 0.4-0.6 part by weight of graphene oxide, reacting at 70-80 ℃ for 2-3h to obtain a graphene oxide modified phenolic resin solution, cooling to 30-40 ℃, adding 0.8-1.2 parts by weight of urea and 0.4-0.5 part by weight of melamine, uniformly mixing at 55-60 ℃, cooling to room temperature, adding 0.1-0.3kg of ammonium sulfate, and uniformly stirring to obtain the tackifier.

By adopting the technical scheme, seawater corrosion mainly occurs at the interface of the high-strength glass fiber cloth and the organic silicon resin, so that the bonding property of the interface is improved, the seawater corrosion resistance of the synthetic leather can be improved, and the service life of the synthetic leather is prolonged.

The phenolic resin in the tackifier is solidified into a network structure, the urea and the volatile micromolecule free formaldehyde in the phenolic resin react to form the non-volatile macromolecular monomer urea-formaldehyde resin, the formaldehyde content can be reduced, the bonding fastness is improved, the melamine can improve the reaction activity of the phenolic resin, can also react with the free formaldehyde, the formaldehyde content is reduced, in addition, the melamine can also react with the hydroxymethyl phenol and the hydroxymethyl urea in the phenolic resin, the bonding strength is improved, so the urea and the melamine can further reduce the formaldehyde content, and simultaneously the bonding strength of the phenolic resin and the high-strength glass fiber cloth is improved; the graphene oxide and the phenolic resin generate intercalation, and reduced graphene oxide is formed under the action of urea and melamine, so that the graphene oxide is uniformly dispersed in the phenolic resin, the hydrophobicity of the phenolic resin is improved, the graphene oxide can be coated on the surface of the fiber on the surface of the high-strength glass fiber cloth, the acting force between the phenolic resin matrix and the glass fiber on the surface of the high-strength glass fiber cloth is enhanced, the reduced graphene oxide with a network structure can increase the porosity of the adhesive layer, and the adhesive layer is prevented from influencing the air permeability of the synthetic leather.

In a second aspect, the application provides a preparation method of organic silicon synthetic leather for decoration of furniture of ships and yachts, which adopts the following technical scheme:

a preparation method of organic silicon synthetic leather for decoration of furniture of ships and yachts comprises the following steps:

preparing synthetic leather slurry: uniformly kneading phenyl vinyl silicone resin, vinyl silicone oil, vinyl fluorosilicone oil, hydrogen-containing silicone oil, a silane coupling agent, a polymerization inhibitor, a platinum catalyst and a low-temperature toughening agent to prepare synthetic leather slurry;

manufacturing of synthetic leather: and coating the synthetic leather slurry on release paper, then compounding the release paper with the base layer, vulcanizing, and stripping the release paper to prepare the synthetic leather.

By adopting the technical scheme, the synthetic leather slurry is firstly coated on the release paper and then compounded with the base layer, and the preparation method is simple and easy to operate.

In summary, the present application has the following beneficial effects:

1. the synthetic leather is prepared from phenyl vinyl silicone resin, vinyl fluorosilicone oil, a low-temperature flexibilizer and other components, wherein the phenyl vinyl silicone resin has surface energy of bottom crossing, the prepared organic silicon has good hydrophobicity, strong yellowing resistance and aging resistance, the low-temperature flexibilizer is prepared from epoxy resin, polyaryletherketone, nano boehmite powder and ultrahigh molecular weight polyethylene, the epoxy resin and the ultrahigh molecular weight polyethylene have the advantages of high low-temperature toughness and low embrittlement temperature, the nano boehmite powder can form a microstructure for absorbing fracture energy between the epoxy resin and the polyaryletherketone, and the nano boehmite powder and the polyaryletherketone have a synergistic effect and are matched with each other, so that low-temperature crack expansion can be effectively prevented, and the low-temperature toughness of the synthetic leather is improved.

2. Preferably adopt EVA and island fibre, collagen fiber, organic modified montmorillonite preparation antiseptic in this application, because EVA has better water blocking, hinder the oxygen nature, and island fibre and collagen fiber are crosslinked each other, form three-dimensional network, and three-dimensional network hole is less, moisture is difficult for passing through, island fibre itself has better gas permeability in addition, thereby EVA's gas permeability has been improved, EVA and organic modified montmorillonite have hydrophobicity simultaneously, thereby make the antiseptic have ventilative and hydrophobic effect, can prevent that the sea water from wetting or permeating inside the synthetic leather at the synthetic leather surface, thereby prevent that sea water or microorganism wherein from causing the influence to the life of synthetic leather.

3. According to the method, the high-strength glass fiber cloth is treated in a mode of sequentially carrying out acid etching and coupling agent spraying, then the adhesive is coated between the high-strength glass fiber cloth and the synthetic leather slurry, the tackifier in the adhesive is prepared from graphene oxide, phenolic resin, urea and melamine, the melamine and the urea can improve the bonding strength of the adhesive and the high-strength glass fiber cloth, and seawater is prevented from permeating from the interface of the high-strength glass fiber cloth and the adhesive layer to corrode; in addition, the graphene oxide can increase the porosity of the adhesive, so that the integral air permeability of the synthetic leather is not influenced.

Detailed Description

Preparation examples 1 to 5 of Low temperature toughener

Preparation examples 1-7 the ultra high molecular weight polyethylene was selected from Jiangsu Jie plastic import & export Co., Ltd under the designation GUR 5113; the nano boehmite powder is selected from new materials of Yangzhou Zhongtianli, and the model is ZTL-BH; the epoxy resin is bisphenol A type solid epoxy particles, is selected from Guangzhou Tianjun chemical industry Co., Ltd, and has the model of E-20; the polyaryletherketone is selected from Shanghai Hongming International trade company, and has a trade mark of AV-651GF30 BK;

preparation example 1: (1) dissolving 5kg of ultra-high molecular weight polyethylene in 8kg of decalin, adding 1.5kg of nano boehmite powder, uniformly mixing, and spinning to prepare ultra-high molecular weight polyethylene fibers;

(2) mixing 3kg of epoxy resin and 1kg of polyaryletherketone, melting at 360 ℃, soaking the ultrahigh molecular weight polyethylene fiber prepared in the step (1) in the melted mixture of the epoxy resin and the polyaryletherketone, solidifying and crushing to prepare the low-temperature toughening agent.

Preparation example 2: (1) dissolving 6.5kg of ultra-high molecular weight polyethylene in 9kg of decalin, adding 2.2kg of nano boehmite powder, uniformly mixing, and spinning to prepare ultra-high molecular weight polyethylene fibers;

(2) mixing 4kg of epoxy resin and 1.5kg of polyaryletherketone, melting at 350 ℃, soaking the ultrahigh molecular weight polyethylene fiber prepared in the step (1) in the melted mixture of the epoxy resin and the polyaryletherketone, solidifying and crushing to prepare the low-temperature toughening agent.

Preparation example 3: (1) dissolving 8kg of ultra-high molecular weight polyethylene in 10kg of decalin, adding 3kg of nano boehmite powder, uniformly mixing, and spinning to prepare ultra-high molecular weight polyethylene fibers;

(2) mixing 5kg of epoxy resin and 2kg of polyaryletherketone, melting at 355 ℃, soaking the ultrahigh molecular weight polyethylene fiber prepared in the step (1) in the melted mixture of the epoxy resin and the polyaryletherketone, solidifying and crushing to prepare the low-temperature toughening agent.

Preparation example 4: the difference from preparation example 1 is that the ultra-high molecular weight polyethylene fiber in step (2) is pretreated by the following steps before impregnation: soaking the ultra-high molecular weight polyethylene fiber in an acid solution at the temperature of 40 ℃ for 50min, and then drying at the temperature of 100 ℃, wherein the mass ratio of the ultra-high molecular weight polyethylene fiber to the acid solution is 1:3, and the acid solution comprises the following components in percentage by weight: 10% of sulfuric acid, 70% of potassium permanganate and 20% of ammonium 2-acrylate.

Preparation example 5: the difference from preparation example 1 is that the ultra-high molecular weight polyethylene fiber in step (2) is pretreated by the following steps before impregnation: soaking the ultra-high molecular weight polyethylene fiber in an acid solution at the temperature of 80 ℃ for 40min, and then drying at the temperature of 130 ℃, wherein the mass ratio of the ultra-high molecular weight polyethylene fiber to the acid solution is 1:5, and the acid solution comprises the following components in percentage by weight: 50% of sulfuric acid, 40% of potassium permanganate and 10% of ammonium 2-acrylate.

Preparation examples 6 to 14 of preservatives

The EVA of preparation examples 6 to 14 was selected from Shanghai Chunyi engineering plastics Co., Ltd, having a product number of 40W; the collagen fiber is selected from Lin Yixin Sheng friction material Co., Ltd, and the model is JY-01; COPET is selected from new Shaoxing-like textile science and technology company with the product number of JR-1; the PET is selected from Dongho plastic raw material Co., Ltd, Dongguan city, and the trade name is CH-610; the vinyltriethoxysilane is selected from Qianan chemical company, Inc. of Guangzhou, model number A-151.

Preparation example 6: mixing 1kg of EVA, 0.1kg of sea island fiber, 0.3kg of collagen fiber and 0.2kg of organic modified montmorillonite, extruding at 80 ℃, granulating to obtain the composite material, wherein the mass ratio of the EVA to the sea island fiber to the collagen fiber to the organic modified montmorillonite is 1:0.1:0.3:0.2, the sea island fiber is prepared by respectively pre-crystallizing and drying COPET and PET with the mass ratio of 4:6, mixing, spinning and cooling, and then soaking for 70min by using a sodium hydroxide solution with the concentration of 1% and the temperature of 100 ℃, and the organic modified montmorillonite is prepared by intercalating octadecyl trimethyl ammonium bromide.

Preparation example 7: mixing 1kg of EVA, 0.3kg of sea island fiber, 0.5kg of collagen fiber and 0.3kg of organic modified montmorillonite, extruding at 90 ℃, and granulating, wherein the mass ratio of the EVA to the sea island fiber to the collagen fiber to the organic modified montmorillonite is 1:0.3:0.5:0.3, and the organic modified montmorillonite is prepared by intercalating octadecyl trimethyl ammonium bromide.

Preparation example 8: mixing 1kg of EVA, 0.5kg of sea island fiber, 0.7kg of collagen fiber and 0.5kg of organic modified montmorillonite, extruding at 100 ℃, and granulating to obtain the composite material, wherein the mass ratio of the EVA to the sea island fiber to the collagen fiber to the organic modified montmorillonite is 1:0.5:0.7:0.5, and the organic modified montmorillonite is prepared by intercalating octadecyl trimethyl ammonium bromide.

Preparation example 9: the difference from preparation example 6 is that sea-island fiber and collagen fiber were not added.

Preparation example 10: the difference from preparation example 6 is that the sea-island fiber was used in an amount of 1kg and the gel coat fiber was used in an amount of 1.5 kg.

Example 11: the difference from preparation example 6 is that no EVA was added.

Preparation example 12: the difference from preparation example 6 is that no organically modified montmorillonite was added.

Preparation example 13: the difference from preparation example 6 is that the organic modified montmorillonite is prepared by the following method:

(1) adding 0.5kg of montmorillonite into 8kg of ethanol solution, performing ultrasonic dispersion for 30min, adding 1.5kg of ammonia water with the mass concentration of 15% and 3kg of ethyl orthosilicate, reacting for 24h, performing suction filtration, performing ultrasonic dispersion in distilled water for 10min, repeating suction filtration and ultrasonic dispersion in distilled water for 3 times, and drying at 50 ℃ for 24h to obtain an intermediate;

(2) 0.5kg of the intermediate was mixed with 3kg of absolute ethanol, 4kg of ammonia water and 4kg of vinyltriethoxysilane, stirred at 30 ℃ for 12h, centrifuged, washed 3 times with absolute ethanol and dried at 50 ℃ for 24 h.

Preparation example 14: the difference from preparation example 6 is that the organic modified montmorillonite is prepared by the following method:

(1) adding 1kg of montmorillonite into 10kg of ethanol solution, performing ultrasonic dispersion for 40min, adding 2kg of ammonia water with the mass concentration of 25% and 4kg of ethyl orthosilicate, reacting for 20h, performing suction filtration, performing ultrasonic dispersion for 20min in distilled water, repeating the suction filtration and the ultrasonic dispersion for 5 times in the distilled water, and drying for 20h at 60 ℃ to obtain an intermediate;

(2) 1kg of intermediate was mixed with 5kg of absolute ethanol, 5kg of ammonia water and 8kg of vinyltriethoxysilane, stirred at 40 ℃ for 10h, centrifuged, washed 5 times with absolute ethanol and dried at 60 ℃ for 20 h.

Preparation examples 15 to 19 of tackifiers

The phenolic resin in preparation examples 15-19 is selected from new chemical technology of Ji-nan Dai Hui, model number 2123; the graphene oxide is selected from Qingdao rock sea carbon material, and the model is YSQ-10; the melamine is selected from the chemical industry of Minghao, Wujiang, with a product number of MH-00121; the urea is selected from Guansu actual Co, Lianhong, with a product number of GS-013.

Preparation example 15: mixing 1kg of phenolic resin and 0.4kg of graphene oxide, reacting for 3h at 70 ℃ to obtain a graphene oxide modified phenolic resin solution, cooling to 30 ℃, adding 0.8kg of urea and 0.4kg of melamine, mixing for 50min at 55 ℃, cooling to room temperature, adding 0.1kg of ammonium sulfate, and uniformly stirring to obtain the tackifier.

Preparation example 16: mixing 2kg of phenolic resin and 0.5kg of graphene oxide, reacting for 2.5h at 75 ℃ to obtain a graphene oxide modified phenolic resin solution, cooling to 35 ℃, adding 1kg of urea and 05kg of melamine, mixing for 40min at 60 ℃, cooling to room temperature, adding 0.2kg of ammonium sulfate, and stirring uniformly to obtain the tackifier.

Preparation example 17: mixing 3kg of phenolic resin and 0.6kg of graphene oxide, reacting for 2h at 80 ℃ to obtain a graphene oxide modified phenolic resin solution, cooling to 40 ℃, adding 1.2kg of urea and 0.5kg of melamine, mixing for 40min at 60 ℃, cooling to room temperature, adding 0.3kg of ammonium sulfate, and uniformly stirring to obtain the tackifier.

Preparation example 18: the difference from preparation example 15 is that no graphene oxide was added.

Preparation example 19: the difference from preparation 15 is that no melamine and no urea are added.

Examples

The phenyl vinyl silicone resin in the following examples is selected from Ningbo Runzhe Gao New materials science and technology Co., Ltd, and the brand is SP 605-3; the vinyl fluorosilicone oil is selected from Guangzhou great-longevity chemical raw material limited company with the model number of 8013-1000; the vinyl silicone oil is selected from Changzhou Polyexcellent new material science and technology company, and the model is JY-205; the hydrogen-containing silicone oil is selected from terminal hydrogen-containing silicone oil with model number YS-800H of Hangzhou Sheng Europe plastication Co Ltd; the polymerization inhibitor is selected from Shenzhen Kejunchi scientific and technological limited, the model is HR03, the platinum catalyst is selected from Shenzhen Kejunchi scientific and technological limited, the model is PH-PT5000, the silane coupling agent is selected from Guangdong Luwei New Material scientific and technological limited, the model is KH-550, and the high-strength glass fiber cloth is selected from Hezhong Kejunchi four-way sealing material factory, the model is SDFS.

Example 1: an organic silicon synthetic leather for decorating furniture of ships and yachts comprises a base layer and synthetic leather slurry coated on the base layer, wherein the base layer is high-strength glass fiber cloth, the raw material formula of the synthetic leather slurry is shown in table 1, wherein the vinyl content of phenyl vinyl silicone resin is 5.3%, the fluorine content of vinyl fluorosilicone oil is 3%, the viscosity of the vinyl fluorosilicone oil is 1000mPa.s, the vinyl content of vinyl silicone oil is 2%, and the viscosity of the vinyl silicone oil is 2000mPa.s, and the low-temperature toughening agent is prepared from preparation example 1.

The preparation method of the organic silicon synthetic leather for decorating the furniture of the ships and yachts comprises the following steps:

s1, preparing synthetic leather slurry: kneading phenyl vinyl silicone resin, vinyl silicone oil, vinyl fluorosilicone oil, cyanide-containing silicone oil, a silane coupling agent, a polymerization inhibitor, a platinum catalyst and a low-temperature toughening agent at 130 ℃ for 2 hours, and vacuumizing and stirring for 20min to prepare synthetic leather slurry;

s2, manufacturing of synthetic leather: coating the synthetic leather slurry on release paper, wherein the coating amount is 150g/m²Then compounding with high-strength glass fiber cloth, vulcanizing at 100 ℃ for 10min, and stripping release paper to prepare the synthetic leather.

Table 1 raw material ratio of organic silicon synthetic leather in examples 1 to 5

Examples 2 to 5: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in example 1 in that the raw material formula is shown in Table 1.

Examples 6 to 9: the organic silicon synthetic leather for decorating the furniture of the ships and the yachts is different from the organic silicon synthetic leather in the example 1 in the preparation example of the low-temperature toughening agent, and the specific selection is shown in the table 2.

TABLE 2 selection of examples for preparation of low temperature tougheners in examples 6-9

Examples	Preparation example of Low-temperature toughening agent
		Example 6	Preparation example 2
Example 7	Preparation example 3
		Example 8	Preparation example 4
Example 9	Preparation example 5

Example 10: an organosilicon synthetic leather for decoration of furniture of ships and yachts, which is different from example 9 in that 2kg of preservative is added to the synthetic leather slurry before kneading, the preservative being prepared by preparation example 6.

Example 11: an organosilicon synthetic leather for decoration of furniture of ships and yachts, which is different from example 10 in that 5kg of preservative is added to the synthetic leather slurry before kneading, the preservative being prepared by preparation example 7.

Examples 12 to 18: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in the example 10 in the preparation example of the preservative, and the specific selection is shown in the table 3.

Table 3 preparation options for preservatives in examples 10-18

Example 19: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in embodiment 18 in that an adhesive layer formed by curing an adhesive is further coated between a high-strength glass fiber cloth and a synthetic leather slurry layer, the raw material formula of the adhesive is shown in Table 4, wherein a tackifier is prepared from preparation example 15, a silicone rubber-based adhesive is prepared from 5kg of low-viscosity vinyl silicone oil, 5kg of high-viscosity vinyl silicone oil, 3kg of white carbon black, 1kg of hexamethyldisilazane, 1kg of aluminum oxide and 1kg of water, the viscosity of the low-viscosity vinyl silicone oil is 1000cs, the vinyl content is 0.5%, the viscosity of the high-viscosity vinyl silicone oil is 50000cs, and the vinyl content is 0.05%.

The preparation method of the organic silicon synthetic leather for ship and yacht furniture decoration comprises the following steps:

s1, pretreatment of the high-strength glass fiber cloth: soaking the high-strength glass fiber cloth in a hydrogen peroxide solution with the concentration of 25% for 20min, taking out, cleaning with distilled water, drying, spraying a silane coupling agent, standing for 80s, and drying, wherein the spraying amount of the silane coupling agent is 25% of the mass of the high-strength glass fiber cloth;

s2, preparation of the adhesive: weighing silicon rubber-based rubber, hydrogen-containing silicon oil, a tackifier, a platinum catalyst and a polymerization inhibitor according to the proportion in the table 4, kneading for 2 hours at 120 ℃ to prepare an adhesive;

s3, preparing synthetic leather slurry: kneading phenyl vinyl silicone resin, vinyl silicone oil, vinyl fluorosilicone oil, cyanide-containing silicone oil, a silane coupling agent, a polymerization inhibitor, a platinum catalyst and a low-temperature toughening agent at 130 ℃ for 2 hours, and vacuumizing and stirring for 20min to prepare synthetic leather slurry;

s4, manufacturing of synthetic leather: coating the synthetic leather slurry on release paper, wherein the coating amount is 150g/m²Baking at 140 deg.C for 5min to form synthetic leather slurry layer, coating adhesive on the synthetic leather slurry layer with coating amount of 120g/m²Compounding with the high-strength glass fiber cloth prepared in the step S1, vulcanizing at 100 ℃ for 10min, and peeling off release paper to prepare the synthetic leather.

TABLE 4 raw material ratios of adhesives in examples 19 to 21

Examples 20 to 21: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in example 18 in that the raw material formula is shown in Table 4.

Example 22: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in example 19 in that the tackifier in the adhesive is prepared from the preparation example 16.

Example 23: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in example 19 in that the tackifier in the adhesive is prepared by the preparation example 17.

Example 24: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in example 19 in that the tackifier in the adhesive is prepared from the preparation example 18.

Example 25: the organic silicon synthetic leather for decorating the furniture of the ships and yachts is different from the organic silicon synthetic leather in example 19 in that the tackifier in the adhesive is prepared from the organic silicon synthetic leather in the preparation example 19.

Example 26: an organosilicon synthetic leather for decorating furniture of ships and yachts, which is different from the organosilicon synthetic leather in example 19 in that high-strength glass fiber cloth is not pretreated in step S1.

Comparative example

Comparative example 1: the organic silicon synthetic leather for decorating the furniture of the ships and the yachts is different from the organic silicon synthetic leather in the embodiment 1 in that the nanometer boehmite powder is used for replacing polyaryletherketone in an equal amount.

Comparative example 2: the organic silicon synthetic leather for decorating the furniture of the ships and the yachts is different from the organic silicon synthetic leather in the embodiment 1 in that the nanometer boehmite powder is equivalently replaced by the polyaryletherketone.

Comparative example 3: the organic silicon synthetic leather for decorating the furniture of the ships and the yachts is different from the organic silicon synthetic leather in the embodiment 1 in that polyaryletherketone and nano boehmite powder are not added.

Comparative example 4: the organic silicon synthetic leather for decorating the furniture of the ships and the yachts is different from the organic silicon synthetic leather in the embodiment 1 in that the ultra-high molecular weight polyethylene is not added.

Comparative example 5: a yacht leather comprises a bottom layer and a foaming layer, wherein the bottom layer comprises 100 parts of PVC resin powder, 80 parts of diisodecyl phthalate, 8 parts of zinc hydroxystannate, 31 parts of aluminum hydroxide, 1 part of an ultraviolet absorbent, 3 parts of a heat stabilizer, 2 parts of an amine inhibitor and 0.7 part of a mildew preventive, the ultraviolet absorbent is phenyl ortho-hydroxybenzoate, the heat stabilizer is a calcium-zinc stabilizer, the amine inhibitor is sodium perchlorate, and the mildew preventive is sodium pentachlorophenate;

the foaming layer comprises 100 parts of PVC resin powder, 75 parts of diisodecyl phthalate, 3 parts of zinc hydroxystannate, 65 parts of aluminum hydroxide, 3 parts of a heat stabilizer, 0.4 part of a mildew preventive, 3 parts of a foaming agent and 1.4 parts of a foam stabilizer, wherein the heat stabilizer is a calcium-zinc stabilizer, the mildew preventive is sodium pentachlorophenate, the foaming agent is an AC foaming agent, and the foam stabilizer is dimethyl silicone oil.

The preparation method of the yacht leather comprises the following steps:

1) respectively mixing and stirring the raw materials of the foaming layer and the bottom layer according to the proportion to obtain a foaming layer mixture and a bottom layer mixture;

2) grinding the foaming layer mixture and the bottom layer mixture in the step 1);

3) defoaming the foaming layer mixture and the bottom layer mixture in the step 2);

4) coating the mixture of the bottom layer on the base fabric for plasticizing, and then coating the mixture of the foaming layer on the bottom layer for foaming.

5) Then the finished product is obtained through surface treatment and embossing.

Performance test

Firstly, detecting the performance of the adhesive: pretreating the high-strength glass fiber cloth according to the method in the embodiment 19, coating the adhesive in the embodiments 19 to 25 on release paper, then respectively compounding with the pretreated high-strength glass cloth, drying for 10min at 100 ℃, and removing the release paper; in example 26, the samples obtained in examples 19 to 26 were tested for peel strength between the adhesive layer and the high strength glass fiber cloth in examples 19 to 26 according to GB/T2791-1995 "flexible material to flexible material by adhesive T peel strength test method", which is denoted as W, without pretreating the high strength glass fiber cloth, as compared with example 19, and the test results are recorded in table 5 according to astm d 1141: 1998 Standard specification for Artificial seawater (appendix A), the samples prepared in examples 19 to 26 were placed in artificial seawater, and after 50 days of immersion at 27. + -. 6 ℃ the peel strength of the samples was measured again and calculated as M and the rate of decrease in peel strength as N, which was calculated according to the following formula: n (%) - (W-M)/W × 100%.

TABLE 5 Peel Strength test of adhesives and high Strength glass fiber cloths in examples 19-26

In the embodiments 19 to 21, the raw materials of the adhesive with different proportions are used, and the prepared adhesive has high peel strength with the pretreated high-strength glass fiber cloth, and after being soaked in seawater, the adhesive still has good peel strength, strong seawater corrosion performance and high peel strength retention rate.

In examples 22 to 23, the tackifiers prepared in preparation examples 16 and 17 were used, respectively, and similarly to example 19, the adhesive strength between the adhesive and the high-strength glass fiber cloth was high, and the peel strength retention rate was high after immersion in seawater, and the corrosion resistance was good.

In example 24, compared to example 19, the adhesion promoter did not contain graphene oxide, and the peel strength between the adhesive layer and the high-strength glass fiber cloth was not much different from that in example 19, but the peel strength was significantly reduced after soaking in seawater, indicating that graphene oxide can enhance the water repellency of the adhesive layer, prevent seawater permeation, and enhance the adhesive strength between the adhesive layer and the high-strength glass fiber cloth base layer.

In example 25, compared with example 19, the peel strength between the adhesive layer and the high-strength glass fiber cloth was significantly reduced before the sea water immersion compared with example 19 without adding urea and melamine to the tackifier, and the rate of reduction of the peel strength was significantly increased after the sea water immersion, indicating that urea and melamine can increase the adhesive strength of the adhesive, make the adhesive layer less susceptible to corrosion by sea water, and the rate of reduction of the peel strength was smaller,

in example 26, the initial peel strength between the adhesive layer and the high-strength glass fiber cloth was significantly reduced compared to example 19 without pretreatment of the high-strength glass fiber cloth, the peel strength after immersion in seawater was significantly reduced, and the rate of reduction in peel strength was greater than example 19, which indicates that the bond strength between the pretreated high-strength glass fiber cloth and the adhesive layer was high and seawater corrosion was prevented.

Secondly, detecting the performance of the synthetic leather:

synthetic leather was prepared according to the methods in the examples and comparative examples, and the properties of the synthetic leather were measured according to the following methods, and the results are reported in table 6.

1. Contact angle: placing the synthetic leather on a video optical contact angle measuring instrument to measure the static contact angle of the surface of the synthetic leather, adopting 5 mu L water drops to test, testing 5 different positions of each synthetic leather fabric, and taking the average value of the positions as the final test result

2. Water vapor permeability: testing according to ASTM E96, Material moisture vapor Permeability test;

3. air permeability: detecting according to GB/T4689.22-1996 leather air permeability determination method;

4. low temperature folding endurance: the prepared synthesized sample pieces are cut into sample pieces with the size of 45mm multiplied by 70mm, wherein the number of the radial sample pieces and the number of the latitudinal sample pieces are respectively 5, the sample pieces are arranged on a low-temperature folding resistance tester (Taiwan Honda, China, the model is HT-8043) to be tested, the detection temperature is-30 ℃, and the folding times when cracks appear are recorded.

TABLE 6 Performance testing of synthetic leather

The synthetic leather prepared in the embodiment 1-5 by using the low-temperature flexibilizer prepared in the preparation example 1 is folded at a low temperature of-30 ℃, the number of cracks is more than 7 ten thousand, and the synthetic leather has good low-temperature folding resistance, large air permeability, good air permeability and good hydrophobic effect.

Examples 6-7 differ from example 1 in that the synthetic leathers prepared in examples 6-7 have similar properties to example 1 compared to example 1 using the low temperature tougheners prepared in preparation 2 and preparation 3, respectively.

Examples 8 to 9 compared with example 1, when the low temperature toughening agent was prepared, the ultra-high molecular weight polyethylene fiber was treated with an acid solution in advance, and the low temperature folding resistance of the synthetic leather was further improved compared with example 1.

As can be seen from the data in Table 6, compared with example 9, the preservatives prepared in preparation examples 6 to 8 are respectively added in examples 10 to 12, the low-temperature folding endurance times of the synthetic leather are not much different from that in example 1, but the contact angle is obviously increased, the super-hydrophobic effect is achieved, the water vapor permeability of the synthetic leather is reduced, the air permeability is enhanced, and the addition of the preservative can improve the hydrophobic state of the surface of the synthetic leather, increase the air permeability and reduce the water vapor permeability.

Example 13 is different from example 10 in that the sea-island fiber and collagen fiber are not added when preparing the preservative, and thus the air permeability of the synthetic leather prepared is reduced, and the low-temperature folding endurance is reduced, which shows that the sea-island fiber and collagen fiber can form a cross-linked network, the air permeability of the synthetic leather surface is increased, and the low-temperature toughness is increased.

Example 14 is different from example 10 in that the amount of the sea-island fiber and the collagen fiber is increased when the antiseptic is prepared, and the air permeability and the water vapor permeability of the synthetic leather prepared therefrom are increased, which means that when the sea-island fiber and the collagen fiber are increased, the porosity of the surface of the synthetic leather is increased, and the surface of the synthetic leather is easily permeable to air and water, so that seawater is easily permeated into the synthetic leather, causing corrosion of the synthetic leather or the appearance of mold.

Example 15 is different from example 10 in that, when the preservative is prepared, EVA is not added, the contact angle of the synthetic leather prepared in example 15 is 132.4 °, which is significantly reduced compared to example 9, and the air permeability and water permeability are both increased, and the low-temperature folding endurance number is reduced, the hydrophobic effect of the synthetic leather surface is reduced, seawater is easily wetted on the synthetic leather surface, or the synthetic leather enters the interior, and corrosion or mold occurs, which indicates that EVA can increase the hydrophobic property of the synthetic leather surface, reduce the air permeability and water permeability of the synthetic leather, and enhance the low-temperature folding endurance.

Example 16 compared with example 10, when the preservative was prepared, the organic modified montmorillonite was not added, the contact angle of the synthetic leather prepared in example 16 with water was 137.6 °, and compared with example 9, the contact angle was decreased, and in addition, the water permeability and air permeability were significantly increased, which indicates that the organic modified montmorillonite can enhance the hydrophobicity of the synthetic leather surface and enhance the barrier property of the synthetic leather against water and gas, thereby preventing the corrosion or mildew phenomenon caused by seawater wetting on the synthetic leather surface or entering the synthetic leather interior through permeation.

In examples 17 and 18, the organic modified montmorillonite is prepared by using silica-coated montmorillonite, and compared with example 10, the contact angle of the synthetic leather prepared in examples 17 and 18 with water is further increased, and the water permeability of the synthetic leather is further reduced, which shows that the organic modified montmorillonite prepared by the application can further improve the hydrophobicity of the synthetic leather and reduce the water permeability of the synthetic leather.

The difference between examples 19-21 and example 18 is that the adhesive prepared from different raw material ratios is coated between the synthetic leather slurry layer and the high-strength glass fiber cloth, and the comparison shows that the contact angle between the synthetic leather surface and water is not greatly different from that of example 18, the low-temperature folding-resistant times are not greatly changed, the air permeability is not remarkably reduced, the water vapor permeability is not obviously increased, and the adhesive layer does not influence the air permeability and the low-temperature folding resistance of the synthetic leather.

In examples 22 to 23, the tackifiers prepared in preparation examples 16 and 17 were used, and synthetic leathers prepared in examples 22 and 23 had better low-temperature folding resistance and air permeability, which indicates that the tackifiers prepared from different raw materials had little influence on the air permeability and low-temperature folding resistance of the synthetic leathers.

In example 24, compared to example 19, the air permeability of the synthetic leather produced in example 24 was decreased without adding graphene oxide to the tackifier, indicating that graphene oxide can improve the porosity of the adhesive layer and increase the air permeability.

In example 25, compared with example 19, the tackifier does not contain urea and melamine, and the synthetic leather prepared in example 25 has high surface hydrophobicity, excellent low-temperature folding resistance, good air permeability and low moisture permeability, which shows that the influence of melamine and urea on the air permeability and the low-temperature folding resistance of the synthetic leather is not significant.

In example 26, compared with example 19, the high-strength glass fiber cloth was not pretreated, and the synthetic leather had the same hydrophobicity as example 19, and was excellent in low-temperature folding resistance and air permeability.

In comparative example 1, the same amount of nano boehmite powder is used to replace polyaryletherketone, namely nano boehmite powder is not added, compared with example 1, the synthetic leather prepared by the comparative example has reduced low-temperature folding resistance, and the synthetic leather is folded 64750 times at-30 ℃ to generate microcracks.

In comparative example 2, the same amount of polyaryletherketone is used to replace the nano boehmite powder, so that the synthetic leather has cracks when the folding times of the synthetic leather at-30 ℃ are 58500 times, and the low-temperature resistance is reduced.

In comparative example 3, the nano boehmite powder and the polyaryletherketone are not used at the same time, and it can be seen from the data in table 6 that microcracks appear when the synthetic leather is folded for 52500 times at-30 ℃, which indicates that the polyaryletherketone and the nano boehmite powder have a good synergistic effect and can improve the cold resistance of the synthetic leather together.

In comparative example 4, in which no ultra-high molecular weight polyethylene was used, microcracks appeared by 61050 folds at-30 ℃ and the low-temperature folding resistance was remarkably reduced, as compared with example 1.

Comparative example 5 is prior art yacht leather with reduced surface hydrophobicity and low temperature folding resistance compared to example 1 and less air permeability.

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.