CN109651945B - Preparation method and application method of high-physical-property graphene-based leather finishing agent - Google Patents
Preparation method and application method of high-physical-property graphene-based leather finishing agent Download PDFInfo
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- CN109651945B CN109651945B CN201811383945.0A CN201811383945A CN109651945B CN 109651945 B CN109651945 B CN 109651945B CN 201811383945 A CN201811383945 A CN 201811383945A CN 109651945 B CN109651945 B CN 109651945B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/16—Esters of inorganic acids
- C09D101/18—Cellulose nitrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of leather-making chemistry and engineering, and provides a preparation method and an application method of a high-physical-property graphene-based leather finishing agent. The polyacrylate, the polyurethane resin and the polysiloxane are used as carriers to prepare the graphene-based leather finishing agent of a stable homogeneous system, so that the dispersion stability of the graphene oxide in the polyacrylate, the polyurethane resin and the polysiloxane is effectively improved, and the advantages of the polyacrylate, the polyurethane resin, the polysiloxane and the graphene are complemented; the obtained leather finishing agent is coated on the surface of leather to form a layer of uniform film containing graphene on the surface of the leather, so that the performance of the leather coating is improved.
Description
Technical Field
The invention relates to the technical field of leather-making chemistry and engineering, in particular to a preparation method and an application method of a high-physical-property graphene-based leather finishing agent.
Background
The leather coating is a very important workshop section in the leather manufacturing process, the leather which is not coated has rough hand feeling and is easy to damage, a layer of film is formed on the surface of the leather after the leather is coated, the hand feeling is smooth, and the leather has certain strength and is difficult to damage. Because of the limitation of leather chemicals, the leather products widely applied at present have the technical defects of poor coating strength, wear resistance, aging resistance and the like, and the current situation seriously restricts the competitiveness of the leather products in the international market in China, so the research and development of the high-performance key technology of the leather products are increased, the traditional leather industry is improved by utilizing high and new technologies, and the method is the key for improving the technical content and the international market competitiveness of the leather products in China and ensuring the advantages of the leather industry in China and the sustainable development of the industry.
At present, in order to solve the foregoing technical problems, ethylene glycol ether is used as a dispersion medium to prepare a graphene dispersion liquid with a graphene content of 0.1%, and then the graphene dispersion liquid is added to a leather finishing agent by a physical blending method to prepare a graphene-based leather finishing agent, and the graphene-based leather finishing agent is applied to a finishing section of a cattle nappa vamp by a spraying method. Although the graphene is a two-dimensional nano material with the highest natural strength and has very good toughness, the application of the graphene in the leather finishing agent is beneficial to improving the strength, the wear resistance and the like of a finishing coating; however, the conventional method has the following problems:
1. in the existing method, the graphene takes ethylene glycol monoethyl ether as a dispersion medium, and the ethylene glycol monoethyl ether is an organic solvent, so that VOC can be generated, harm is generated to human health, and the requirement of environmental protection and leather making is not met; moreover, the graphene has the technical defect of reaction inertia, is difficult to react with components of a leather finishing agent or leather collagen fibers, and can be agglomerated and deposited on the surface of the leather along with gradual volatilization of ethylene glycol ethyl ether, so that the graphene is not uniformly distributed and is easy to peel off, the defect of different wear-resisting strength of coatings at different parts of the surface of the leather is shown, the film forming stability of the finishing agent is reduced, and the practical finishing effect is reduced; the prepared finishing agent is a heterogeneous system, has poor stability and is not storage-resistant;
2. the leather finishing agent is a multi-component mixture and comprises polyacrylate, polyurethane resin and other non-resin components, the phenomenon that graphene is adsorbed with the polyacrylate and the polyurethane resin and is also adsorbed with the non-resin components can be caused by directly adding and mixing the graphene dispersion liquid and the leather finishing agent in the prior art, the wear resistance of a coating is mainly determined by the performances of the polyacrylate and the polyurethane resin in the leather finishing agent, and the graphene adsorbed with the non-resin components cannot play an effective role, so that the production problems of low effective utilization rate of the graphene, cost increase and the like are caused.
3. The graphene has the technical defects of easy agglomeration, reaction inertia and the like, so that the graphene is difficult to be directly dispersed into a polymer system, the graphene is difficult to be functionally modified, and the acting force between the graphene and the polymer only has van der walls force, so that the physicochemical property of the material is not obviously improved; compared with graphene, although graphene oxide can be well dispersed in a polymer system, the physical and chemical properties of graphene oxide are obviously reduced compared with graphene mixture because the two-dimensional structure of graphene oxide is destroyed.
4. The physical blending method is adopted for composite mixing, the graphene or the graphene oxide and the polymer are combined through van der walls force, the main chain of the leather finishing agent polymer is completely composed of single bonds, the single bonds are good in flexibility, so that the potential barrier delta mu b for conversion among polymer space conformations is far smaller than the external field action energy, the polymer monomers are randomly coiled in a coil shape in the space, and the polymer chain segment can continuously change the conformation. Because the intermolecular acting force is far weaker than the covalent bond bonding, the flexibility of the polymer chain segment is too strong, graphene or graphene oxide is difficult to be well anchored on the polymer by relying on van der walls force, the dispersibility of the graphene or the graphene oxide in the polymer is too weak, the promotion of the physicochemical property is limited, precipitates or suspension liquid is easy to form, the comprehensive performance of the composite material is greatly reduced, and the practicability is low.
Disclosure of Invention
Therefore, in order to solve the problems, the invention provides a preparation method and an application method of the high-physical-property graphene-based leather finishing agent. The preparation method of the high-physical-property graphene-based leather finishing agent adopts the graphene oxide, the graphene oxide has oxygen-containing groups, is good in water solubility and reactivity, can react with hydroxyl, carboxyl or amino groups in polyacrylate, polyurethane resin and polysiloxane or can be combined with the hydroxyl, carboxyl or amino groups in leather collagen fibers, and is not easy to fall off. The leather finishing agent with a stable homogeneous system is prepared by taking polyacrylate, polyurethane resin and polysiloxane as carriers, so that the dispersion stability of graphene oxide in the polyacrylate, the polyurethane resin and the polysiloxane is effectively improved, and the advantages of the polyacrylate, the polyurethane resin, the polysiloxane and the graphene are complemented; the obtained leather finishing agent is coated on the surface of leather to form a layer of uniform film containing graphene on the surface of the leather, so that the performance of the leather coating is improved.
In order to realize the technical problem, the solution scheme adopted by the invention is as follows: a preparation method of a high-physical-property graphene-based leather finishing agent comprises the steps of dissolving graphene-based polysiloxane emulsion, graphene oxide-based polyacrylate resin emulsion, graphene oxide-based polyurethane resin emulsion and a finishing auxiliary agent in water, and performing ultrasonic dispersion to prepare the graphene-based leather finishing agent; the graphene-based polysiloxane emulsion is prepared by performing sol-gel reaction, reduction and emulsification compounding on graphene oxide grafted modified polysiloxane; the graphene oxide-based polyacrylate resin emulsion is obtained by grafting graphene oxide on modified polyacrylate resin; the graphene oxide-based polyurethane resin emulsion is obtained by grafting graphene oxide onto a modified polyurethane resin.
The preparation method of the high-physical-property graphene-based leather finishing agent specifically comprises the following steps:
step 1, preparing modified polysiloxane: reacting a siloxane monomer, a silane coupling agent, an end-capping agent, a catalyst and a crosslinking agent at 70-140 ℃ for 3-8h to obtain modified polysiloxane;
step 2, preparing modified graphene oxide: adding graphene oxide into a solvent, adding N, N-dicyclohexylcarbodiimide, performing ultrasonic dispersion for 20-270min to obtain a modified graphene oxide precursor dispersion liquid, transferring the modified graphene oxide precursor dispersion liquid into a reactor, adding a modifier, reacting for 12-96h at 50-150 ℃, adding absolute ethyl alcohol with the same amount as the solvent, standing for 6-48h at 0-50 ℃, filtering, washing, performing vacuum drying to obtain solid powder, and reducing to obtain modified graphene oxide;
step 3, preparation of graphene-based polysiloxane: adding the modified graphene oxide obtained in the step 2 into deionized water, and performing ultrasonic dispersion for 20-200min to obtain a modified graphene oxide dispersion liquid; adding the modified polysiloxane obtained in the step 1 into the modified graphene oxide dispersion liquid, adding triethylamine, reacting at the temperature of 10-50 ℃ for 3-8h to obtain sol, and then heating to 60-100 ℃ to react for 1-5h to obtain a gel aqueous solution; drying the gel aqueous solution in vacuum to obtain gel, and reducing to obtain graphene-based polysiloxane;
step 4, preparing the graphene-based polysiloxane emulsion: mixing two or more different emulsifiers, and then dispersing and stirring for 5-120min to obtain an emulsifier mixed solution; uniformly mixing the graphene modified polysiloxane obtained in the step 3 with polysiloxane to obtain a polysiloxane mixed solution; adding the polysiloxane mixed solution into the emulsifier mixed solution, and dispersing and stirring for 5-120min to obtain a reaction mixed solution; dropwise adding 5-15 times of deionized water into the reaction mixed solution in a dispersing and stirring state to obtain emulsion; adding 0-20% of auxiliary emulsion into the emulsion, and dispersing and stirring for 5-120min to obtain graphene-based polysiloxane emulsion;
step 5, preparing the graphene oxide-based polyacrylate resin emulsion: dissolving graphene oxide powder in water, performing ultrasonic dispersion, then adjusting the pH to 6.5-9 by using 2-4% ammonia water to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid with polyacrylate resin emulsion, and performing ultrasonic dispersion to prepare graphene oxide-based polyacrylate resin emulsion with the graphene oxide concentration of 0.05-0.1%;
step 6, preparing the graphene oxide-based polyurethane resin emulsion: dissolving graphene oxide powder in water, performing ultrasonic dispersion, then adjusting the pH to 6.5-9 by using 2-4% ammonia water to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid with polyurethane resin emulsion, and performing ultrasonic dispersion to prepare graphene oxide-based polyurethane resin emulsion with the mass fraction of graphene oxide of 0.05-0.1%;
step 7, preparing the graphene-based leather finishing agent: according to the parts by weight, 0-160 parts of graphene oxide base polyacrylate resin emulsion, 0-125 parts of graphene oxide base polyurethane resin emulsion, 0-15 parts of graphene base polysiloxane emulsion and a coating auxiliary agent are dissolved in water and dispersed by ultrasonic waves to prepare the graphene base leather coating agent.
Wherein, the siloxane monomer in the step 1 is octamethylcyclotetrasiloxane.
Wherein, the silane coupling agent in the step 1 is at least one of 3-chloropropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2,3 epoxypropoxy) propyltriethoxysilane and triethoxysilane.
Wherein, the end-capping agent in the step 1 is at least one of 1, 3-bis (3-glycidyloxypropyl) -1,1,3, 3-tetramethyldisiloxane and hexamethyldisiloxane.
Wherein, the catalyst in the step 1 is at least one of potassium hydroxide, lithium hydroxide and tetramethyl ammonium hydroxide.
Wherein, the cross-linking agent in the step 1 is at least one of epoxypropanol and epoxypropyl chloride.
Wherein, in the step 1, the concentration of the silane coupling agent is 0.1-5%, the concentration of the blocking agent is 0.1-1%, the concentration of the catalyst is 0.01-0.2%, and the concentration of the crosslinking agent is 0-4%.
Wherein, the modifier in the step 2 is polyethylene polyamine or silane coupling agent; the solvent is an organic solvent or a silane coupling agent.
The polyethylene polyamine is at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine, and the silane coupling agent is one of 3-chloropropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2,3 epoxypropoxy) propyltriethoxysilane and triethoxysilane.
The organic solvent is at least one of N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the silane coupling agent is one of 3-chloropropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2,3 epoxypropoxy) propyltriethoxysilane and triethoxysilane.
Wherein, in the step 2, the concentration of the graphene oxide in the solvent is 0.5-10g/L, the concentration of the N, N-dicyclohexylcarbodiimide in the solvent is 1-15g/L, and the concentration of the modifier in the solvent is 0-500 g/L.
Wherein the concentration of the modified graphene oxide in the deionized water in the step 3 is 0.5-10 g/L; the concentration of the modified polysiloxane in the modified graphene oxide dispersion liquid is 100-1000g/L, and the concentration of the triethylamine in the modified graphene oxide dispersion liquid is 0.005-0.025 g/L.
Wherein, the emulsifier in the step 4 is at least one of TWEEN20, TWEEN 40, TWEEN 60, TWEEN 80, SPAN 20, SPAN 40, SPAN 60, SPAN80, OP 10, OP40, TX10 and TX 100.
Wherein, the polysiloxane in the step 4 is at least one of hydroxyl polysiloxane, amino polysiloxane, epoxy polysiloxane and methyl polysiloxane; the viscosity of the polysiloxane is 100-10000 mPas.
Wherein, the proportion of the polysiloxane in the graphene modified polysiloxane in the step 4 is 0-100%; the concentration of the polysiloxane mixed solution in the emulsifier mixed solution is 10-90%.
Wherein, the auxiliary emulsion in the step 4 is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and n-pentanol.
Wherein the finishing auxiliary agent in the step 7 comprises casein, an auxiliary agent and pigment paste, and the graphene-based leather finishing agent prepared in the step 7 is a middle-layer graphene-based leather finishing agent;
step 7, preparing the graphene-based leather finishing agent: according to the parts by weight, 125-160 parts of graphene oxide-based polyacrylate resin emulsion, 85-100 parts of graphene oxide-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of auxiliary agent and 65-80 parts of pigment paste are dissolved in 300-450 parts of water, and the middle-layer graphene-based leather finishing agent is prepared through ultrasonic dispersion.
Wherein the finishing auxiliary agent in the step 7 comprises a nitrocotton brightener, a polyurethane brightener, a wax auxiliary agent and a cross-linking agent, and the graphene-based leather finishing agent prepared in the step 7 is an upper graphene-based leather finishing agent;
step 7, preparing the graphene-based leather finishing agent: according to the parts by weight, 0-150 parts of nitrocotton brightener, 0-150 parts of polyurethane brightener, 5-20 parts of oil wax auxiliary agent, 5-20 parts of graphene-based polysiloxane emulsion and 2-7 parts of cross-linking agent are dissolved in 100-200 parts of water and dispersed by ultrasonic waves to prepare the upper graphene-based leather finishing agent.
Wherein the graphene-based leather finishing agent prepared in the step 7 is a top layer graphene-based leather finishing agent;
step 7, preparing the graphene-based leather finishing agent: according to the weight portion, 7-12 portions of graphene-based polysiloxane emulsion are dissolved in 80-150 portions of water, and ultrasonic dispersion is carried out to obtain the top layer graphene-based leather finishing agent.
The application method of the high-physical-property graphene-based leather finishing agent is characterized by sequentially comprising the following steps of: crust leather bottoming coating → ironing → middle layer graphene-based leather coating → ironing → upper layer graphene-based leather coating → drying → ironing → vibration softening → vibration softening → stretching plate drying → ironing → top layer graphene-based leather coating → drying → ironing → dry vacuum; the middle-layer graphene-based leather finishing agent comprises the following components in parts by weight: 125-160 parts of oxidized graphene-based polyacrylate resin emulsion, 85-100 parts of oxidized graphene-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of an auxiliary agent, 65-80 parts of a pigment paste and 300-450 parts of water; the upper graphene-based leather finishing agent comprises the following components in parts by weight: 0-150 parts of nitrocotton brightener, namely 0-150 parts of polyurethane brightener, 5-20 parts of oil wax additive, 5-20 parts of graphene-based polysiloxane emulsion, 2-7 parts of cross-linking agent and 100 parts of water by weight; the top graphene-based leather finishing agent comprises the following components in parts by weight: 7-12 parts of graphene-based polysiloxane emulsion and 80-150 parts of water.
Wherein the coating amount of the middle-layer graphene-based leather finishing agent coating is 10-15 g/sf; the coating amount of the upper graphene-based leather finishing agent coating is 5-10 g/sf; the coating amount of the top graphene-based leather finishing agent coating is 2-5 g/sf; the ironing condition is 120-; the intensity of the oscillation softening is 5-6 levels; the milling time is 8-12 h; the drying condition of the toggling plate is 45-50 ℃/4-6cm/20-25min, and the dry vacuum condition is 65-80 ℃/15-30 seconds/vacuum degree- (0.05-0.1) MPa.
By adopting the technical scheme, the invention has the beneficial effects that: compared with the prior art, the preparation method of the high-physical-property graphene-based leather finishing agent has the following advantages:
1. water is used as a dispersion medium, so that no VOC is generated, and the method is green and environment-friendly and meets the requirement of environmental protection and leather making; the graphene oxide is a reactive material, can react with hydroxyl, carboxyl or amino in polyacrylate, polyurethane resin and polysiloxane or can be combined with hydroxyl, carboxyl or amino of leather collagen fiber, and is not easy to fall off, and the prepared graphene-based leather finishing agent is a homogeneous system, has good stability and is storage-resistant; the finishing agent is coated on the surface of the leather and gradually volatilizes along with water, and the graphene oxide can be uniformly distributed on the surface of the leather and firmly combined, so that the characteristic of consistent coating performance at different parts of the surface of the leather is shown.
2. The graphene oxide takes polyacrylate and polyurethane resin as carriers to form a stable homogeneous system, the effect is obvious, and the graphene oxide dispersion liquid is compounded with the polyacrylate and polyurethane resin emulsion and then added into the coating agent, so that the effective utilization rate of the graphene oxide can be greatly improved, and the cost is reduced.
3. Chemically grafting polyacrylate, polyurethane resin and polysiloxane by using graphene oxide covalent bond functional modification as an active site. The functionalized graphene oxide not only can further improve the dispersion stability of the lamellar layer of the functionalized graphene oxide in various solvents and polymers, but also can obviously improve the compatibility of the functionalized graphene oxide and the polymers after functionalized graphene oxide modified by covalent bonds is introduced into functionalized molecules, polymers and groups, so that the functionalized graphene oxide can be better and more uniformly dispersed in the functionalized molecules, polymers and other matrixes.
4. Polyacrylate, polyurethane resin and polysiloxane are grafted on graphene oxide by a chemical grafting method, the graphene oxide is bonded with a polymer through a chemical bond, the graphene oxide is uniformly dispersed in the polymer, meanwhile, an active site on the graphene oxide enables the polymer to be branched to a certain degree and blocks rotation of a chain, intermolecular forces such as a conjugated pi bond and a hydrogen bond are formed between the polymer and the graphene oxide through an active group introduced by a modifier, and the dispersion stability of the graphene oxide in the polymer is further improved.
5. The modified graphene oxide is reduced, so that the original graphene structure of the graphene oxide is recovered, and only a small amount of oxygen-containing functional groups exist on the edge of the graphene oxide.
6. The graphene-based leather finishing agent is used for leather finishing, so that the strength, the wear resistance and the aging resistance of a leather coating are greatly improved, the tearing strength of the leather coating is improved by 8-12%, and the elongation at break is reduced by 6-8%; the wear resistance of the leather coating is improved by 16-18%; the ageing resistance of the leather coating is improved by 4-8%, and the waterproof performance is not permeable for 48 h.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, so that how to apply technical means to solve technical problems and achieve technical effects can be fully understood and implemented, and it should be noted that the embodiments are only used for further description of the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and adjustments according to the above disclosure.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. Various procedures and methods not described in detail are conventional methods well known in the art, and the source, trade name, and if necessary, the constituents of the reagents used are indicated at the first appearance.
Example 1
A preparation method of a high-physical-property graphene-based leather finishing agent comprises the following steps:
step 1, preparing modified polysiloxane: reacting a siloxane monomer (octamethylcyclotetrasiloxane), a silane coupling agent (3-aminopropyltriethoxysilane), an end-capping agent (1, 3-bis (3-glycidyloxypropyl) -1,1,3, 3-tetramethyldisiloxane) and a catalyst (tetramethylammonium hydroxide) at 90 ℃ for 6 hours to obtain modified polysiloxane; wherein the concentration of the silane coupling agent is 2%, the concentration of the blocking agent is 0.8%, and the concentration of the catalyst is 0.06%;
step 2, preparing modified graphene oxide: adding graphene oxide (single-layer graphene oxide) into a silane coupling agent (3-chloropropyl triethoxysilane), wherein the concentration of the graphene oxide in the silane coupling agent is 7.5g/L, then adding N, N-dicyclohexyl carbodiimide, wherein the concentration of the N, N-dicyclohexyl carbodiimide in the silane coupling agent is 7.5g/L, ultrasonically dispersing for 90min (the ultrasonic dispersion power is 60W) to obtain a graphene oxide dispersion liquid, transferring the graphene oxide dispersion liquid into a reactor to react for 36h at 70 ℃, filtering, washing, vacuum drying (the vacuum drying temperature is 35 ℃, the drying time is 60h) the reaction mixture liquid to obtain solid powder, and reducing (the reduction method is to reduce 2.5% hydrazine hydrate solution for 8h) to obtain modified graphene oxide;
step 3, preparation of graphene-based polysiloxane: adding the modified graphene oxide obtained in the step (2) into deionized water, wherein the concentration of the modified graphene oxide in the deionized water is 2g/L, and performing ultrasonic dispersion for 90min (the ultrasonic dispersion power is 60W) to obtain a modified graphene oxide dispersion liquid; adding the modified polysiloxane obtained in the step 1 into a modified graphene oxide dispersion solution, wherein the concentration of the modified polysiloxane in the modified graphene oxide dispersion solution is 350g/L, adding triethylamine, the concentration of the triethylamine in the modified graphene oxide dispersion solution is 0.02g/L, reacting at 25 ℃ for 3 hours to prepare sol, then heating to 80 ℃ to react for 3 hours to prepare a gel aqueous solution, carrying out vacuum drying on the gel aqueous solution (the vacuum drying temperature is 35 ℃, and the drying time is 60 hours) to obtain gel, and reducing (the reduction method is to carry out reduction treatment for 8 hours by using 2.5% hydrazine hydrate solution) to obtain graphene-based polysiloxane;
step 4, preparing the graphene-based polysiloxane emulsion: mixing 65 parts of emulsifier TWEEN20 and 35 parts of emulsifier SPAN80, and performing ultrasonic dispersion for 10min (the ultrasonic action power is 600W) to obtain an emulsifier mixed solution; uniformly mixing the graphene oxide modified polysiloxane obtained in the step 3 with polysiloxane (methyl polysiloxane, the viscosity of which is 500mPa & s) to obtain a polysiloxane mixed solution, wherein the ratio of the polysiloxane in the graphene oxide modified polysiloxane is 85%; adding the polysiloxane mixed solution into the emulsifier mixed solution, wherein the concentration of the polysiloxane mixed solution in the emulsifier mixed solution is 65%, and performing ultrasonic dispersion for 60min (the ultrasonic action power is 600W) to obtain a reaction mixed solution; dropwise adding 9 times of deionized water into the reaction mixed solution in a dispersing and stirring state to obtain emulsion; adding 5% of auxiliary emulsion (n-amyl alcohol) into the emulsion, and performing ultrasonic dispersion for 60min (the ultrasonic action power is 600W) to obtain graphene-based polysiloxane emulsion;
step 5, preparing the graphene oxide-based polyacrylate resin emulsion:
dissolving 10.0 parts of graphene oxide powder in 1000 parts of water, performing ultrasonic dispersion for 30min at the ultrasonic power of 300W, and then adjusting the pH to 7.5 by using 2% ammonia water to prepare graphene oxide dispersion liquid;
mixing 8 parts of graphene oxide dispersion liquid with 500 parts of polyacrylate resin emulsion (RA-2356, the solid content is 20%, Statel Fine paint (Suzhou) Co., Ltd.), and ultrasonically dispersing for 30min at the ultrasonic power of 450W to prepare graphene oxide-based polyacrylate resin emulsion RA-2356 with the graphene oxide mass fraction of 0.08%;
mixing 14 parts of graphene oxide dispersion liquid with 500 parts of polyacrylate resin emulsion (RA-1079, the solid content is 35%, Statel Fine coating (Suzhou) Co., Ltd.), and ultrasonically dispersing for 30min at the ultrasonic power of 500W to obtain graphene oxide-based polyacrylate resin emulsion RA-1079 with the graphene oxide mass fraction of 0.08%;
step 6, preparing the graphene oxide-based polyurethane resin emulsion:
dissolving 10.0 parts of graphene oxide powder in 1000 parts of water, performing ultrasonic dispersion for 30min at the ultrasonic power of 300W, and then adjusting the pH to 7.5 by using 2% ammonia water to prepare graphene oxide dispersion liquid;
mixing 14 parts of the graphene oxide dispersion liquid obtained in the step 1 with 500 parts of polyurethane resin emulsion (RU-3910, the solid content is 35%, and the Steyr fine coating (Suzhou) Co., Ltd.), and performing ultrasonic dispersion for 30min at the ultrasonic power of 500W to obtain graphene oxide-based polyurethane resin emulsion RU-3910 with the graphene oxide mass fraction of 0.08%;
mixing 14 parts of the graphene oxide dispersion liquid obtained in the step 1 with 500 parts of polyurethane resin emulsion (Aqualen Top LN.A, the solid content is 35%, Stal Fine paint (Suzhou) Co., Ltd.), and performing ultrasonic dispersion for 30min at the ultrasonic power of 500W to obtain graphene oxide-based polyurethane resin emulsion Aqualen Top LN.A with the graphene oxide mass fraction of 0.08%;
step 7, preparing the graphene-based leather finishing agent:
dissolving 60 parts of graphene oxide-based polyacrylate resin emulsion, 80 parts of graphene oxide-based polyacrylate resin emulsion RA-1079, 100 parts of graphene oxide-based polyurethane resin emulsion, 60 parts of casein (RODA bound TU688/B, Delry leather chemical Co., Ltd.), 40 parts of wax additive (48416-GAA, Shanghai Pilereflies chemical Co., Ltd.), 50 parts of softening additive (EUDERM Nappa SoftS-C, Langsheng group), 80 parts of pigment paste (PPE DEEP BLACK A-ID, Stahl fine paint (Suzhou)) in 400 parts of water, stirring for 8min at a stirring speed of 950r/min to prepare a middle-layer graphene-based leather finishing agent;
② 100 parts of nitrocotton brightener (WL-8119, Shanghai Feng Wanwei leather chemical Co., Ltd.), 10 parts of oil wax additive (KO 2311, Xiamen HaoDeya trade Co., Ltd.), 10 parts of graphene-based polysiloxane emulsion and 5 parts of cross-linking agent (Aqualen AKU liq, Steyr fine paint (Suzhou) Co., Ltd.) are dissolved in 150 parts of water and stirred for 8min at the stirring speed of 950r/min to prepare the upper graphene-based leather finishing agent.
Dissolving 10 parts of graphene-based polysiloxane emulsion in 100 parts of water, and stirring for 8min at the stirring speed of 950r/min to obtain the top layer graphene-based leather finishing agent.
Application example 1
An application method of a high-physical-property graphene-based leather finishing agent sequentially comprises the following steps: crust leather bottoming coating → ironing → coating of middle layer graphene-based leather coating obtained in example 1 → ironing → coating of upper layer graphene-based leather coating obtained in example 1 → drying → ironing → shaking softening → stretching plate drying → ironing → coating of top layer graphene-based leather coating obtained in example 1 → drying → ironing → dry vacuum; wherein the coating amount of the middle-layer graphene-based leather finishing agent coating is 15 g/sf; the coating amount of the middle-layer graphene-based leather finishing agent coating is 8 g/sf; the coating amount of the top graphene-based leather finishing agent coating is 3 g/sf; the ironing condition is 120 ℃/30 kgf; the intensity of the oscillation softening is 5 levels; the milling time is 10 h; the drying condition of the toggling plate is 50 ℃/4cm/25min, and the dry vacuum condition is 80 ℃/15 seconds/vacuum degree-0.1 MPa.
After the graphene-based leather finishing agent is coated, the tearing strength of a leather coating is improved by 8-12%, and the elongation at break is reduced by 6-8%; the wear resistance of the leather coating is improved by 16-18%; the ageing resistance of the leather coating is improved by 4-8%, and the waterproof performance is not permeable for 48 h.
In conclusion, the preparation method and the application method of the high-physical-property graphene-based leather finishing agent introduce the graphene oxide nano material as the reinforcing agent of the leather coating aiming at the technical defects of poor strength, wear resistance and aging resistance of the traditional leather coating, the graphene oxide has higher specific surface area and more abundant oxygen-containing functional groups, and can be blended with polyacrylate, polyurethane resin and polysiloxane leather film-forming agent under the action of ultrasonic waves to prepare the graphene-based leather finishing film-forming agent with good uniformity and stability; the graphene oxide has excellent strength and toughness, so that the mechanical properties of polyacrylate, polyurethane resin and polysiloxane leather film-forming agent can be enhanced and toughened, and the high-performance leather coating is obtained.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (21)
1. A preparation method of a high-physical-property graphene-based leather finishing agent is characterized by comprising the following steps: dissolving graphene-based polysiloxane emulsion, graphene oxide-based polyacrylate resin emulsion, graphene oxide-based polyurethane resin emulsion and a coating auxiliary agent in water, and performing ultrasonic dispersion to obtain a graphene-based leather coating agent; the graphene-based polysiloxane emulsion is prepared by performing sol-gel reaction, reduction and emulsification compounding on graphene oxide grafted modified polysiloxane; the graphene oxide-based polyacrylate resin emulsion is obtained by grafting graphene oxide on modified polyacrylate resin; the graphene oxide-based polyurethane resin emulsion is obtained by grafting graphene oxide onto a modified polyurethane resin.
2. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 1, characterized by comprising the following steps:
step 1, a preparation method of modified polysiloxane: reacting a siloxane monomer, a silane coupling agent, an end-capping agent, a catalyst and a crosslinking agent at 70-140 ℃ for 3-8h to obtain modified polysiloxane;
step 2, a preparation method of the modified graphene oxide comprises the following steps: adding graphene oxide into a solvent, adding N, N-dicyclohexylcarbodiimide, performing ultrasonic dispersion for 20-270min to obtain a modified graphene oxide precursor dispersion liquid, transferring the modified graphene oxide precursor dispersion liquid into a reactor, adding a modifier, reacting for 12-96h at 50-150 ℃, adding absolute ethyl alcohol with the same amount as the solvent, standing for 6-48h at 0-50 ℃, filtering, washing, performing vacuum drying to obtain solid powder, and reducing to obtain modified graphene oxide;
step 3, a preparation method of the graphene-based polysiloxane comprises the following steps: adding the modified graphene oxide obtained in the step 2 into deionized water, and performing ultrasonic dispersion for 20-200min to obtain a modified graphene oxide dispersion liquid; adding the modified polysiloxane obtained in the step 1 into the modified graphene oxide dispersion liquid, adding triethylamine, reacting for 3-8h at 10-50 ℃ to obtain sol, and then heating to 60-100 ℃ to react for 1-5h to obtain a gel aqueous solution; drying the gel aqueous solution in vacuum to obtain gel, and reducing to obtain graphene-based polysiloxane;
step 4, a preparation method of the graphene-based polysiloxane emulsion comprises the following steps: mixing two or more different emulsifiers, and then dispersing and stirring for 5-120min to obtain an emulsifier mixed solution; uniformly mixing the graphene modified polysiloxane obtained in the step 3 with polysiloxane to obtain a polysiloxane mixed solution; adding the polysiloxane mixed solution into the emulsifier mixed solution, and dispersing and stirring for 5-120min to obtain a reaction mixed solution; dropwise adding 5-15 times of deionized water into the reaction mixed solution in a dispersing and stirring state to obtain emulsion; adding 0-20% of auxiliary emulsion into the emulsion, and dispersing and stirring for 5-120min to obtain graphene-based polysiloxane emulsion;
step 5, a preparation method of the graphene oxide-based polyacrylate resin emulsion comprises the following steps: dissolving graphene oxide powder in water, performing ultrasonic dispersion, then adjusting the pH to 6.5-9 by using 2-4% ammonia water to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid with polyacrylate resin emulsion, and performing ultrasonic dispersion to prepare graphene oxide-based polyacrylate resin emulsion with the graphene oxide concentration of 0.05-0.1%;
step 6, a preparation method of the graphene oxide-based polyurethane resin emulsion comprises the following steps: dissolving graphene oxide powder in water, performing ultrasonic dispersion, then adjusting the pH to 6.5-9 by using 2-4% ammonia water to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid with polyurethane resin emulsion, and performing ultrasonic dispersion to prepare graphene oxide-based polyurethane resin emulsion with the mass fraction of graphene oxide of 0.05-0.1%;
step 7, a preparation method of the graphene-based leather finishing agent comprises the following steps: according to the weight portion, 0-160 parts of graphene oxide base polyacrylate resin emulsion, 0-125 parts of graphene oxide base polyurethane resin emulsion, 0-15 parts of graphene base polysiloxane emulsion and a coating auxiliary agent are dissolved in water and are subjected to ultrasonic dispersion to prepare the graphene base leather coating agent, and the dosage of the graphene oxide base polyacrylate resin emulsion, the graphene oxide base polyurethane resin emulsion and the graphene base polysiloxane emulsion is not 0 at the same time.
3. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 1, the siloxane monomer is octamethylcyclotetrasiloxane.
4. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 1, the silane coupling agent is at least one of 3-chloropropyl triethoxysilane, 3-aminopropyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl triethoxysilane and triethoxysilane.
5. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 1, the end-capping reagent is at least one of 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane and hexamethyldisiloxane.
6. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 1, the catalyst is at least one of potassium hydroxide, lithium hydroxide and tetramethyl ammonium hydroxide.
7. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 1, the cross-linking agent is at least one of epoxypropanol and epoxypropylchloride.
8. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 1, the concentration of the silane coupling agent is 0.1-5%, the concentration of the blocking agent is 0.1-1%, the concentration of the catalyst is 0.01-0.2%, and the concentration of the crosslinking agent is 0-4%.
9. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 2, the modifier is polyethylene polyamine or silane coupling agent; the solvent is an organic solvent or a silane coupling agent.
10. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 9, wherein the preparation method comprises the following steps: the polyethylene polyamine is at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine, and the silane coupling agent is at least one of 3-chloropropyl triethoxysilane, 3-aminopropyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl triethoxysilane and triethoxysilane.
11. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 9, wherein the preparation method comprises the following steps: the organic solvent is at least one of N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the silane coupling agent is at least one of 3-chloropropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane and triethoxysilane.
12. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 2, the concentration of the graphene oxide in the solvent is 0.5-10g/L, the concentration of the N, N-dicyclohexylcarbodiimide in the solvent is 1-15g/L, and the concentration of the modifier in the solvent is 0-500 g/L.
13. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 3, the concentration of the modified graphene oxide in deionized water is 0.5-10 g/L; the concentration of the modified polysiloxane in the modified graphene oxide dispersion liquid is 100-1000g/L, and the concentration of the triethylamine in the modified graphene oxide dispersion liquid is 0.005-0.025 g/L.
14. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 4, the emulsifier is at least one of TWEEN20, TWEEN 40, TWEEN 60, TWEEN 80, SPAN 20, SPAN 40, SPAN 60, SPAN80, OP 10, OP40, TX10 and TX 100.
15. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 4, the polysiloxane is at least one of hydroxyl polysiloxane, amino polysiloxane, epoxy polysiloxane and methyl polysiloxane; the viscosity of the polysiloxane is 100-10000 mPas.
16. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 4, the proportion of the polysiloxane in the graphene modified polysiloxane is 0-100%; the concentration of the polysiloxane mixed solution in the emulsifier mixed solution is 10-90%.
17. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: in the step 4, the auxiliary emulsion is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and n-pentanol.
18. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: the finishing auxiliary agent in the step 7 comprises casein, an auxiliary agent and pigment paste, and the graphene-based leather finishing agent prepared in the step 7 is a middle-layer graphene-based leather finishing agent;
step 7, the preparation method of the graphene-based leather finishing agent comprises the following steps: according to the parts by weight, 125-160 parts of graphene oxide-based polyacrylate resin emulsion, 85-100 parts of graphene oxide-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of auxiliary agent and 65-80 parts of pigment paste are dissolved in 300-450 parts of water, and the middle-layer graphene-based leather finishing agent is prepared by ultrasonic dispersion.
19. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: the finishing auxiliary agent in the step 7 comprises a nitrocotton brightener, a polyurethane brightener, a wax oil auxiliary agent and a cross-linking agent, and the graphene-based leather finishing agent prepared in the step 7 is an upper graphene-based leather finishing agent;
step 7, the preparation method of the graphene-based leather finishing agent comprises the following steps: according to the parts by weight, 0-150 parts of nitrocotton brightener, 0-150 parts of polyurethane brightener, 5-20 parts of oil wax auxiliary agent, 5-20 parts of graphene-based polysiloxane emulsion and 2-7 parts of cross-linking agent are dissolved in 100-200 parts of water and dispersed by ultrasonic waves to prepare the upper graphene-based leather finishing agent.
20. The preparation method of the high-physical-property graphene-based leather finishing agent according to claim 2, characterized by comprising the following steps: the graphene-based leather finishing agent prepared in the step 7 is a top layer graphene-based leather finishing agent;
step 7, the preparation method of the graphene-based leather finishing agent comprises the following steps: according to the weight portion, 7-12 portions of graphene-based polysiloxane emulsion are dissolved in 80-150 portions of water, and ultrasonic dispersion is carried out to obtain the top layer graphene-based leather finishing agent.
21. An application method of a high-physical-property graphene-based leather finishing agent is characterized by sequentially comprising the following steps of: crust leather bottoming coating → ironing → middle layer graphene-based leather coating → ironing → upper layer graphene-based leather coating → drying → ironing → vibration softening → vibration softening → stretching plate drying → ironing → top layer graphene-based leather coating → drying → ironing → dry vacuum; the middle-layer graphene-based leather finishing agent comprises the following components in parts by weight: 125-160 parts of oxidized graphene-based polyacrylate resin emulsion, 85-100 parts of oxidized graphene-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of an auxiliary agent, 65-80 parts of a pigment paste and 300-450 parts of water; the upper graphene-based leather finishing agent comprises the following components in parts by weight: 0-150 parts of nitrocotton brightener, 0-150 parts of polyurethane brightener, 5-20 parts of oil wax additive, 5-20 parts of graphene-based polysiloxane emulsion, 2-7 parts of cross-linking agent and 100-200 parts of water; the top graphene-based leather finishing agent comprises the following components in parts by weight: 7-12 parts of graphene-based polysiloxane emulsion and 80-150 parts of water.
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