阅读说明：本技术 石墨烯高物性合成革、制备方法及设备 (Graphene high-physical-property synthetic leather, preparation method and equipment ) 是由 郑重 刘爱明 罗志清 梁勇劲 刘格 于 2019-11-01 设计创作，主要内容包括：本发明公开了石墨烯高物性合成革、制备方法及设备,石墨烯高物性合成革,其由以下组成制成：染色坯革、石墨烯粉、浓硫酸、高锰酸钾、聚氨酯预聚体、-OH的改性石墨烯单体、成盐剂及去离子水,本发明还公开了石墨烯高物性合成革的制备方法,包括以下步骤：S1：进行石墨烯亲水改性,S2：亲油改性及引入活性基团,S3：制备聚氨酯预聚体,S4：得到水性聚氨酯乳液涂饰剂,S5：进行涂饰。本发明的制备方法更加的科学合理,有效提高皮革的耐磨耐刮性,耐水解能力强,抗菌抗霉,对金黄色葡萄球菌、肺炎克雷伯氏菌、大肠杆菌、混合霉菌等均具有良好的抑杀作用,抗菌率大于99％,防霉等级达1-0级,同时制备设备在制备过程中对物料加热均匀,提高了制备质量。(The invention discloses graphene high-physical-property synthetic leather, a preparation method and equipment, wherein the graphene high-physical-property synthetic leather is prepared from the following components: the invention also discloses a preparation method of the graphene high-physical-property synthetic leather, which comprises the following steps of: s1: carrying out graphene hydrophilic modification, and carrying out S2: lipophilic modification and introduction of active groups, S3: preparing a polyurethane prepolymer, S4: obtaining the aqueous polyurethane emulsion coating agent, S5: and (7) coating. The preparation method is more scientific and reasonable, effectively improves the wear resistance and the scratch resistance of the leather, has strong hydrolysis resistance, resists bacteria and mildew, has good inhibiting and killing effects on staphylococcus aureus, klebsiella pneumoniae, escherichia coli, mixed mildew and the like, has the antibacterial rate of more than 99 percent, achieves the mildew prevention level of 1-0 level, and simultaneously ensures that the preparation equipment uniformly heats materials in the preparation process and improves the preparation quality.)

1. High rerum natura synthetic leather of graphite alkene, characterized by that, it is made up of following: the production process comprises the following steps of dyeing crust leather, graphene powder, concentrated sulfuric acid, potassium permanganate, polyurethane prepolymer, -OH modified graphene monomer, salt forming agent and deionized water.

2. The preparation method of the graphene high-physical-property synthetic leather according to claim 1, which is characterized by comprising the following steps of:

s1: carrying out hydrophilic modification on graphene, and mixing graphene powder, concentrated sulfuric acid and potassium permanganate to obtain graphene oxide;

s2: oleophylic modification and introduction of active groups, and hydrophilic modification of graphene is carried out, and then-COOH, epoxy group and other active groups are introduced, so that the hydrophilicity is improved, and reaction points are provided for oleophylic modification;

s3: preparing a polyurethane prepolymer, heating polyester or polyether polyol and a small molecular chain extender to 50 ℃, adding isocyanate and a catalyst for stirring, heating to 70 ℃, reacting for two hours, heating to 75 ℃, adding the chain extender, and reacting until-NCO reaches a theoretical value to obtain the polyurethane prepolymer;

s4: adding a certain amount of-OH-containing modified graphene monomer into the prepolymer, reacting at 50 ℃ for 1 hour, adding a salt forming agent for neutralization for 30 minutes, and adding deionized water under strong stirring for emulsification to obtain a waterborne polyurethane emulsion coating agent;

s5: and (7) coating.

3. The preparation method of the graphene high-physical-property synthetic leather according to claim 2, characterized by comprising the following steps: in S1, the concentration of concentrated sulfuric acid was 98%.

4. The preparation method of the graphene high-physical-property synthetic leather according to claim 2, characterized by comprising the following steps: in S1, the particle size of the graphene powder is less than 30 microns, and the mass fraction of carbon is 99.9%.

5. The preparation method of the graphene high-physical-property synthetic leather according to claim 2, characterized by comprising the following steps: in S2, graphene oleophylic modification and introduction of double bond, -OH and other active groups lay a foundation for development of graphene-based leather finishing agents.

6. The preparation method of the graphene high-physical-property synthetic leather according to claim 2, characterized by comprising the following steps: in S4, stirring is not stopped during the emulsification process of adding deionized water.

7. The preparation method of the graphene high-physical-property synthetic leather according to claim 2, characterized by comprising the following steps: in S5, the coating process sequentially includes the steps of: dyed crust leather → staking → graphene-containing polyurethane primer → drying → midway → drying → graphene-containing resin surface coating → drying → milling → finished leather.

8. The equipment for preparing the graphene high-physical-property synthetic leather by implementing the method in any one of claims 2 to 7 comprises a kettle body (1), and is characterized in that: the corner positions of the outer surface of the lower end of the kettle body (1) are fixedly provided with support legs (2), a motor (3) is movably arranged in the middle of the outer surface of the upper end of the kettle body (1), a feed inlet (4) is arranged on one side of the outer surface of the upper end of the kettle body (1), a thermometer (5) is movably arranged on the other side of the outer surface of the upper end of the kettle body (1), a discharge pipe (6) is movably arranged at the lower end of the outer surface of one side of the kettle body (1), a stirring shaft (7) is movably arranged on the outer surface of the lower end of the motor (3), stirring blades (8) are fixedly arranged on both sides of the stirring shaft (7), inner cavities (9) are arranged inside the stirring shaft (7) and the stirring blades (8), and the stirring shaft (7) is communicated with the stirring blades (8) through an inner cavity (9), and a heating wire (10) is arranged in the inner cavity (9).

9. The preparation equipment of high-physical-property graphene synthetic leather according to claim 8, characterized in that: the thermometer (5) penetrates through the kettle body (1).

10. The preparation equipment of high-physical-property graphene synthetic leather according to claim 8, characterized in that: the motor (3) and the heating wire (10) are electrically connected with an external power supply.

Technical Field

The invention relates to the field of synthetic leather, in particular to graphene high-physical-property synthetic leather, a preparation method and equipment.

Background

The leather coating is a very important workshop section in the leather manufacturing process, leather which is not coated is rough in hand feeling and easy to damage, a layer of film is formed on the surface of the leather after coating, the hand feeling is smooth, the leather has certain strength and is not easy to damage, and the leather product widely applied at present has the technical defects of poor coating strength, wear resistance, aging resistance, antibacterial property, mildew resistance and the like due to the limitation of leather chemicals.

Graphene is a two-dimensional carbon nanomaterial with hexagonal honeycomb lattices formed by sp hybridized orbits of carbon atoms, has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a future revolutionary material.

High rerum natura synthetic leather of graphite alkene usually adopts reation kettle to prepare, but current reation kettle heating methods is usually through heating the inner wall of the cauldron body, then passes to the material for in the cauldron body with the heat, and the center department of this kind of heating methods material does not contact with the inner wall of the cauldron body, leads to easily heating unevenly.

Disclosure of Invention

The invention aims to provide a preparation method of graphene high-physical-property synthetic leather, which aims to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the graphene high-physical-property synthetic leather is prepared from the following components: the production process comprises the following steps of dyeing crust leather, graphene powder, concentrated sulfuric acid, potassium permanganate, polyurethane prepolymer, -OH modified graphene monomer, salt forming agent and deionized water.

The preparation method of the graphene high-physical-property synthetic leather comprises the following steps:

s1: carrying out hydrophilic modification on graphene, and mixing graphene powder, concentrated sulfuric acid and potassium permanganate to obtain graphene oxide;

s2: oleophylic modification and introduction of active groups, and hydrophilic modification of graphene is carried out, and then-COOH, epoxy group and other active groups are introduced, so that the hydrophilicity is improved, and reaction points are provided for oleophylic modification;

s3: preparing a polyurethane prepolymer, heating polyester or polyether polyol and a small molecular chain extender to 50 ℃, adding isocyanate and a catalyst for stirring, heating to 70 ℃, reacting for two hours, heating to 75 ℃, adding the chain extender, and reacting until-NCO reaches a theoretical value to obtain the polyurethane prepolymer;

s4: adding a certain amount of-OH-containing modified graphene monomer into the prepolymer, reacting at 50 ℃ for 1 hour, adding a salt forming agent for neutralization for 30 minutes, and adding deionized water under strong stirring for emulsification to obtain a waterborne polyurethane emulsion coating agent;

s5: and (7) coating.

Preferably, in S1, the concentrated sulfuric acid has a concentration of 98%.

Preferably, in S1, the graphene powder has a particle size of less than 30 microns and a carbon mass fraction of 99.9%.

Preferably, in S2, the graphene oleophylic modification and introduction of double bond, -OH and other active groups lay a foundation for the development of graphene-based leather finishing agents.

Preferably, in S4, stirring is not stopped during the emulsification process by adding deionized water.

Preferably, in S5, the coating process includes the following steps in order: dyed crust leather → staking → graphene-containing polyurethane primer → drying → midway → drying → graphene-containing resin surface coating → drying → milling → finished leather.

The preparation equipment of the graphene high-physical-property synthetic leather comprises a kettle body, wherein supporting legs are fixedly arranged at corners of the outer surface of the lower end of the kettle body, a motor is movably arranged at the middle position of the outer surface of the upper end of the kettle body, a charging hole is formed in one side of the outer surface of the upper end of the kettle body, a thermometer is movably arranged at the other side of the outer surface of the upper end of the kettle body, a discharge pipe is movably arranged at the lower end of the outer surface of one side of the kettle body, a stirring shaft is movably arranged at the outer surface of the lower end of the motor, stirring blades are fixedly arranged on two sides of the stirring shaft, inner cavities are formed in the stirring shaft and the stirring blades, the stirring shaft is communicated with the stirring blades through the inner cavities, heating wires are arranged in the inner cavities, graphene powder with the granularity being less than 30 micrometers and the mass fraction of carbon being 99, fully stirring to obtain graphene oxide, introducing active groups such as-COOH, epoxy group and the like into a kettle body to improve hydrophilicity and provide a reaction point for oleophylic modification, introducing active groups such as double bond, OH and the like into the graphene oleophylic modification and laying a foundation for development of a graphene-based leather finishing agent, adding polyester or polyether polyol and a small molecular chain extender into the reaction kettle, heating to 50 ℃, adding isocyanate and a catalyst for stirring, heating to 70 ℃ and reacting for two hours, heating to 75 ℃, adding the chain extender, reacting until-NCO reaches a theoretical value to obtain a polyurethane prepolymer, heating by adopting a heating wire from the inside to heat a stirring shaft and stirring blades, fully contacting the stirring shaft and the stirring blades with the material after being heated to ensure that the material is uniformly heated, detecting the temperature of the material in the kettle body by a thermometer, ensuring that the heating condition of materials can be known in real time in the preparation process, finally, adding a certain amount of-OH-containing modified graphene monomer into the prepolymer, continuously reacting for 1 hour at 50 ℃, then adding a salt forming agent for neutralizing for 30 minutes, adding deionized water under strong stirring for emulsification to obtain a waterborne polyurethane emulsion coating agent, discharging the waterborne polyurethane emulsion coating agent through a discharge pipe after the preparation is finished, and coating the waterborne polyurethane emulsion coating agent on high-physical-property synthetic leather, wherein the coating process sequentially comprises the following steps: dyed crust leather → staking → graphene-containing polyurethane primer → drying → midway → drying → graphene-containing resin surface coating → drying → milling → finished leather.

The leather has the advantages of effectively improving the wear resistance and the scratch resistance of leather, having strong hydrolysis resistance and antibacterial and mildew-resistant performances, having good inhibition and killing effects on staphylococcus aureus, klebsiella pneumoniae, escherichia coli, mixed mildew and the like, having the antibacterial rate of more than 99 percent and the mildew-resistant grade of 1-0, and simultaneously uniformly heating materials in the preparation process of preparation equipment, thereby improving the preparation quality.

Preferably, the thermometer penetrates through the interior of the kettle body, the temperature of the materials in the kettle body is detected through the thermometer, and the heating condition of the materials can be known in real time in the preparation process.

Preferably, electric connection between motor and heater strip all and the external power supply utilizes the motor to drive the (mixing) shaft and rotates, and the stirring leaf rotates along with the (mixing) shaft is synchronous to utilize (mixing) shaft and stirring leaf to stir the material, utilize the heating wire to heat (mixing) shaft and stirring leaf among the stirring process, can be fully with the material contact after (mixing) shaft and stirring leaf are heated, make the material be heated evenly.

Compared with the prior art, the invention has the beneficial effects that: the preparation method is more scientific and reasonable, effectively improves the wear resistance and the scratch resistance of the leather, has strong hydrolysis resistance, resists bacteria and mildew, has good inhibiting and killing effects on staphylococcus aureus, klebsiella pneumoniae, escherichia coli, mixed mildew and the like, has the antibacterial rate of more than 99 percent, achieves the mildew prevention level of 1-0 level, and simultaneously ensures that the preparation equipment uniformly heats materials in the preparation process and improves the preparation quality.

Drawings

FIG. 1 is an overall flow chart of the present invention;

FIG. 2 is a schematic view showing the overall structure of the production apparatus of the present invention;

FIG. 3 is a view showing the combination of a stirring shaft and heating wires of the manufacturing apparatus of the present invention.

In the figure: 1. a kettle body; 2. a support leg; 3. a motor; 4. a feed inlet; 5. a thermometer; 6. a discharge pipe; 7. a stirring shaft; 8. stirring blades; 9. an inner cavity; 10. a heating wire.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to fig. 1 to 3, the present invention provides a technical solution: the graphene high-physical-property synthetic leather is prepared from the following components: the production process comprises the following steps of dyeing crust leather, graphene powder, concentrated sulfuric acid, potassium permanganate, polyurethane prepolymer, -OH modified graphene monomer, salt forming agent and deionized water.

The preparation method of the graphene high-physical-property synthetic leather comprises the following steps:

s1: carrying out hydrophilic modification on graphene, and mixing graphene powder with the particle size of less than 30 microns and the mass fraction of carbon of 99.9%, concentrated sulfuric acid with the concentration of 98% and potassium permanganate to obtain graphene oxide;

s2: oleophylic modification and introduction of active groups, wherein the graphene is subjected to hydrophilic modification and then introduced with-COOH, epoxy and other active groups to improve hydrophilicity and provide reaction points for oleophylic modification, and the graphene is subjected to oleophylic modification and introduced with double bond, -OH and other active groups to lay a foundation for development of a graphene-based leather finishing agent;

s3: preparing a polyurethane prepolymer, adding polyester or polyether polyol and a micromolecular chain extender into a reaction kettle, heating to 50 ℃, adding isocyanate and a catalyst, stirring, heating to 70 ℃, reacting for two hours, heating to 75 ℃, adding the chain extender, and reacting until-NCO reaches a theoretical value to obtain the polyurethane prepolymer;

s4: adding a certain amount of-OH-containing modified graphene monomer into the prepolymer, reacting at 50 ℃ for 1 hour, adding a salt forming agent for neutralization for 30 minutes, and adding deionized water under strong stirring for emulsification to obtain a waterborne polyurethane emulsion coating agent;

s5: coating, wherein the coating process sequentially comprises the following steps: dyed crust leather → staking → graphene-containing polyurethane primer → drying → midway → drying → graphene-containing resin surface coating → drying → milling → finished leather.

Preparation equipment of high rerum natura synthetic leather of graphite alkene, including the cauldron body 1, the equal fixed mounting in lower extreme surface corner position of the cauldron body 1 has stabilizer blade 2, and the upper end surface intermediate position movable mounting of the cauldron body 1 has motor 3, charge door 4 has been seted up to upper end surface one side of the cauldron body 1, and the upper end surface opposite side movable mounting of the cauldron body 1 has thermometer 5, one side surface lower extreme position movable mounting of the cauldron body 1 has row material pipe 6, the lower extreme surface movable mounting of motor 3 has (mixing) shaft 7, and the equal fixed mounting in both sides of (mixing) shaft 7 has stirring leaf 8, inner chamber 9 has all been seted up with stirring leaf 8's inside to (mixing) shaft 7, and (mixing) shaft 7 is linked together through inner chamber 9 with stirring leaf 8, the inside of inner chamber 9 is equipped with heater strip 10, at first is less than 30 microns with the granularity through charge door 4, and the, Adding 98% concentrated sulfuric acid and potassium permanganate into a kettle body 1, mixing, fully stirring to obtain graphene oxide, introducing active groups such as-COOH, epoxy group and the like into the kettle body 1 to improve hydrophilicity, providing reaction points for oleophylic modification, carrying out oleophylic modification on the graphene, introducing active groups such as double bonds and-OH, laying a foundation for development of a graphene-based leather finishing agent, adding polyester or polyether polyol and a small-molecular chain extender into the reaction kettle, heating to 50 ℃, adding isocyanate and a catalyst, stirring, heating to 70 ℃, reacting for two hours, heating to 75 ℃, adding the chain extender, reacting until-NCO reaches a theoretical value to obtain a polyurethane prepolymer, heating by using a heating wire 10, heating a stirring shaft 7 and a stirring blade 8 from the inside, and fully contacting the stirring shaft 7 and the stirring blade 8 with materials after heating, the method comprises the following steps of uniformly heating materials, detecting the temperature of the materials in a kettle body 1 through a thermometer 5, ensuring that the heating condition of the materials can be known in real time in the preparation process, finally adding a modified graphene monomer containing-OH in a measured amount into a prepolymer, continuously reacting at 50 ℃ for 1 hour, then adding a salt forming agent for neutralization for 30 minutes, adding deionized water under strong stirring for emulsification to obtain a waterborne polyurethane emulsion coating agent, discharging the waterborne polyurethane emulsion coating agent through a discharge pipe 6 after the preparation is finished, and coating the waterborne polyurethane emulsion coating agent on high-physical-property synthetic leather, wherein the coating process sequentially comprises the following steps: dyed crust leather → staking → graphene-containing polyurethane primer → drying → midway → drying → graphene-containing resin surface coating → drying → milling → finished leather.

The thermometer 5 penetrates through the interior of the kettle body 1, the temperature of the materials in the kettle body 1 is detected through the thermometer 5, and the heating condition of the materials can be known in real time in the preparation process.

Electric connection between motor 3 and heater strip 10 all and the external power supply utilizes motor 3 to drive (mixing) shaft 7 and rotates, and stirring leaf 8 follows (mixing) shaft 7 and rotates in step to utilize (mixing) shaft 7 and stirring leaf 8 to stir the material, utilize heater strip 10 to heat (mixing) shaft 7 and stirring leaf 8 among the stirring process, can be fully with the material contact after (mixing) shaft 7 and stirring leaf 8 are heated, make the material be heated evenly.

The preparation equipment of the graphene high-physical-property synthetic leather provided by the invention comprises the steps of firstly adding graphene powder with the granularity of less than 30 microns and the carbon mass fraction of 99.9%, concentrated sulfuric acid with the concentration of 98% and potassium permanganate into a kettle body 1 through a feeding port 4, mixing, fully stirring to obtain oxidized graphene, then introducing active groups such as-COOH, epoxy group and the like into the kettle body 1 to improve the hydrophilicity, simultaneously providing a reaction point for oleophylic modification, carrying out oleophylic modification on the graphene and introducing active groups such as double bond, OH and the like to lay a foundation for the development of a graphene-based leather finishing agent, then adding polyester or polyether polyol and a small molecular chain extender into the reaction kettle, heating to 70 ℃ and reacting for two hours, heating to 75 ℃ and adding a chain extender, reacting until-NCO reaches a theoretical value, obtaining a polyurethane prepolymer, heating a stirring shaft 7 and a stirring blade 8 by adopting a heating wire 10 from the inside when the temperature rises, fully contacting the stirring shaft 7 and the stirring blade 8 with materials after the stirring shaft 7 and the stirring blade 8 are heated, enabling the materials to be uniformly heated, detecting the temperature of the materials in a kettle body 1 by using a thermometer 5, ensuring that the heating condition of the materials can be known in real time in the preparation process, finally adding a modified graphene monomer containing-OH in a metering manner into the prepolymer, continuously reacting for 1 hour at 50 ℃, then adding a salt forming agent for neutralizing for 30 minutes, adding deionized water under strong stirring for emulsifying to obtain an aqueous polyurethane emulsion coating agent, discharging the aqueous polyurethane emulsion coating agent through a discharging pipe 6 after the preparation is finished, and coating the aqueous polyurethane emulsion coating agent on high-physical property synthetic leather, wherein the coating process sequentially comprises the following steps: dyed crust leather → staking → graphene-containing polyurethane primer → drying → midway → drying → graphene-containing resin surface coating → drying → milling → finished leather.

The preparation method is more scientific and reasonable, effectively improves the wear resistance and the scratch resistance of the leather, has strong hydrolysis resistance, resists bacteria and mildew, has good inhibiting and killing effects on staphylococcus aureus, klebsiella pneumoniae, escherichia coli, mixed mildew and the like, has the antibacterial rate of more than 99 percent, achieves the mildew prevention level of 1-0 level, and simultaneously ensures that the preparation equipment uniformly heats materials in the preparation process and improves the preparation quality.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.