CN108456482A - A kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of polyurethane decorative paint for leather, a kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent and preparation method thereof is disclosed.The leather finishing agent is made of the two parts separately stored, and first part and second part are all according to mass fraction meter；First part includes following components：25 55 parts of polyalcohol, 29 45 parts of diisocyanate, 3 15 parts of hydrophily glycol chain extender, dihydric alcohol/5 25 parts of trihydroxylic alcohol chain extender, 0.05 1 parts of catalyst, 3 20 parts of neutralizer, 250 450 parts of water, 1 15 parts of graphene, 0.05 3 parts of silane coupling agent；Second part is curing agent；5 15 parts of curing agent.The present invention Aqueous Polyurethane Leather Finishing Agent is with preferable storage stability and water-fast, solvent resistance and polyurethane coating is with preferable mechanics and heat conductivility.

Description

A kind of graphene modified two-component waterborne polyurethane leather finishing agent and preparation method thereof

technical field

The invention belongs to the technical field of polyurethane leather finishing agents, and in particular relates to a graphene-modified two-component water-based polyurethane leather finishing agent and a preparation method thereof.

Background technique

Water-based polyurethane is a new type of polyurethane system that replaces organic solvents with water as the dispersion medium, also known as water-based polyurethane. Compared with traditional solvent-based polyurethane, it not only has the advantages of no pollution, environmental protection and safety, flame retardancy, etc., but also has the characteristics of wear resistance and excellent mechanical strength. It is widely used in coatings, adhesives, inks, leather finishing and other fields . Take leather finishing as an example: finishing is an important process in leather manufacturing. It can make the leather surface look different in color, style and luster, increase the appearance of leather and endow it with certain waterproof performance and easy maintenance, and expand its use. scope. Among them, polyurethane leather finishing agent can obviously improve the quality and grade of leather due to its excellent mechanical properties and hiding power, so it has been widely used. At present, the polyurethane leather finishing agents on the market are mainly one-component water-based polyurethane, which is terminated with isocyanate groups, and then synthesized by internal emulsification with carboxylate or sulfonate as hydrophilic groups. However, the presence of isocyanate makes this type of product have high reactivity at room temperature, which makes the storage stability poor.

Compared with the one-component leather finishing agent, the storage stability of the two-component leather finishing agent of the present invention is better, and the storage stability of water-based polyurethane in the leather finishing agent is further improved by modification; Alcohols are used together, the coating film has high gloss and good adhesion, which can meet the needs of leather finishing of different materials.

Graphene is a honeycomb lattice material composed of a single layer of carbon atoms and only one carbon atom thick. It is currently known as the world's thinnest and hardest new nanomaterial with the strongest electrical/thermal conductivity and the highest strength. Using graphene to modify the two-component polyurethane leather finishing agent can improve the water resistance and solvent resistance of water-based polyurethane. While improving the mechanical properties of the coating agent, it can be used more widely.

Contents of the invention

In order to overcome the shortcomings and deficiencies of the existing one-component leather finishing agent and the water-based polyurethane in the leather finishing agent, the object of the present invention is to provide a graphene-modified two-component water-based polyurethane leather finishing agent. In the present invention, graphene is dispersed into the hydroxyl-terminated water-based polyurethane emulsion for modification, and isocyanate-based curing agent added after it is used for cross-linking, while improving its storage stability, water resistance and solvent resistance, and improving the polyurethane coating. The mechanical and thermal properties of the layer.

Another object of the present invention is to provide a preparation method of the above-mentioned graphene-modified two-component waterborne polyurethane leather finishing agent.

The purpose of the present invention is achieved through the following technical solutions:

A graphene-modified two-component water-based polyurethane leather finishing agent, consisting of two parts stored separately, the first part and the second part are calculated in parts by mass;

The first part includes the following components:

The second part is curing agent;

5-15 parts of curing agent.

The first part also includes a wetting and leveling agent and a feeling agent, and the mass parts of the wetting and leveling agent and the feeling agent are:

The first part also includes an organic solvent, the organic solvent is N,N-dimethylformamide, and the mass ratio of the neutralizing agent to the organic solvent is (3-20):(5-12).

The polyol is one or more of PCL1000, PCL2000, PCL3000, PPG400, PPG1000, PPG2000, and PBA3000, preferably two or more.

Described diisocyanate is isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) trimer, hexamethylene diisocyanate (HDI), toluene diisocyanate One or more types of isocyanate (TDI).

The hydrophilic diol chain extender is more than one of dimethylol propionic acid (DMPA) or dimethylol butyric acid (DMBA).

The dihydric alcohol/trihydric alcohol chain extender is 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerol more than one of .

The catalyst is dibutyltin dilaurate or stannous octoate.

The neutralizing agent is more than one of triethanolamine, triethylamine and sodium hydroxide.

The wetting and leveling agent is one or more of Sliok-8333, Sliok-8858 or Sliok-8035, preferably Sliok-8858.

The hand feeling agent is one or more of Sliok-9151, Sliok-3300, and Sliok-9148, preferably Sliok-3300.

The curing agent is more than one of Perstorp WT2102 and XD803.

The silane coupling agent is one or more of KH-560, KH-570 and KH-164, preferably KH-164.

The amount of graphene is preferably 1-10 parts, more preferably 1-6 parts.

The preparation method of described graphene modified two-component water-based polyurethane leather finishing agent comprises the following steps:

(1) Vacuum dehydration of the polyol, and then react with the diisocyanate under the action of a part of the catalyst, the reaction temperature is 60-80°C, and the reaction time is 1-3 hours, to obtain the prepolymer;

(2) Add hydrophilic diol chain extender to the prepolymer, keep warm for 1-3 hours, add diol/triol chain extender and remaining catalyst, heat up to 70-85°C, and polymerize 2-4 hours, lower the temperature, add a neutralizer and an organic solvent for neutralization, and obtain a polyurethane prepolymer;

(3) Under medium-speed stirring, water is added in the polyurethane prepolymer, and after the water is added, the rotation speed is increased, and emulsified to obtain a hydroxyl-terminated aqueous polyurethane emulsion;

(4) Graphene is mixed with water, drips silane coupling agent, ultrasonic dispersion, obtains graphene dispersion liquid; Graphene dispersion liquid is mixed with the water-based polyurethane emulsion that contains hydroxyl termination, obtains the modified water-based polyurethane emulsion;

(5) When in use, mix the modified water-based polyurethane emulsion with a wetting and leveling agent and a hand feeling agent evenly, and finally add a curing agent to obtain a water-based polyurethane leather finishing agent.

The condition of the vacuum dehydration in step (1) is vacuum drying at 90-110° C. for 0.5-1 hour, and the part of the catalyst is 30-70% of the total amount of the catalyst;

The temperature of the heat preservation reaction in step (2) is 60-80°C; the temperature of the cooling is 35-45°C, and the time of the neutralization reaction is 20-45 minutes;

The rotating speed of medium speed described in step (3) is 800-1200r/min; Said increasing rotating speed refers to rotating rotating speed is increased to 3000-4000r/min; The addition of described water is: water and hydrophilicity two The mass ratio of the alcohol chain extender is (150-350): (3-15), that is, the addition of the water is 150-350 parts by mass; the emulsification time is 15-30min;

The consumption relation of Graphene described in step (4) and water is to add 1-15 mass parts Graphene in every 100 mass parts water; Disperse evenly at a speed of 1/min.

The present invention improves the storage stability of water-based polyurethane by synthesizing polyurethane containing hydroxyl end-capping; meanwhile, different chain extenders are used to adjust the mechanical properties (such as adhesion) of polyurethane; wherein the hydrophilic chain extender is for the polyurethane chain Introduce hydrophilic groups to promote the synthesis of water-based polyurethane emulsion, and at the same time control the water resistance of the coating film. The use of diol/triol chain extenders is to extend the linear/body-shaped chain of the polyurethane chain and adjust its Mechanical properties; the combination of polyols with different molecular weights can make the finished polyurethane leather finishing agent maintain a balance between good adhesion and stickiness; the role of the silane coupling agent is to make graphene evenly dispersed in water under the action of ultrasound phase, and finally uniformly distributed in the polyurethane emulsion under low-speed dispersion; as a surfactant, the silane coupling agent acts as a bridge connecting the organic phase (polyurethane emulsion) and the inorganic phase (graphene), which can make the graphene uniform Dispersed in aqueous polyurethane emulsion.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

In the present invention, graphene is dispersed into the hydroxyl-terminated water-based polyurethane emulsion for modification, and isocyanate-based curing agent added after it is used for cross-linking, while improving its storage stability, water resistance and solvent resistance, and improving the polyurethane coating. The mechanical and thermal properties of the layer. The storage stability of the water-based polyurethane leather finishing agent of the present invention is reflected by the storage stability of the water-based polyurethane emulsion.

Detailed ways

The present invention will be described in further detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto.

Example 1

(1) Add 6.2 parts by mass of molecular weight polycaprolactone diol (PCL1000) and 37.1 parts by mass of polycaprolactone diol (PCL2000) with a molecular weight of 2000 in the reaction vessel, and dry it with a vacuum pump at 105°C for 30 Minutes, after cooling to normal temperature, add 35.7 parts by mass of isophorone diisocyanate and 0.05 parts by mass of catalyst dibutyltin dilaurate, and keep at 80°C for 1 hour;

(2) Add 7 parts by mass of dimethylol propionic acid to the above reactant, heat up to 80°C, and react for 1.5 hours; then add 8.5 parts by mass of 1,4-butanediol (dried and dehydrated in advance), Polymerize for 3.5 hours, then lower the temperature to 42°C, add 5.5 parts by mass of triethylamine and 8 parts by mass of N,N-dimethylformamide that has been dehydrated in advance for neutralization, and the reaction time is 25 minutes to obtain a polyurethane prepolymerized body;

(4) under the rotating speed of disperser 1000r/min, slowly add the deionized level of 200 mass parts in the polyurethane prepolymer, then raise the rotating speed to 3500r/min, emulsify 20min, obtain the waterborne polyurethane emulsion ( Hydroxyl-terminated water-based polyurethane emulsion with blue light);

(5) Place 1 mass part of graphene in 100 mass parts of deionized water, drop 1 mass part of silane coupling agent (KH-164), and ultrasonically disperse for 45min to obtain a stably dispersed graphene dispersion; disperse the graphene Liquid and the polyurethane emulsion containing hydroxyl end-capping are mixed under the disperser effect of 400r/min, obtain modified polyurethane emulsion (the water-based polyurethane emulsion containing hydroxyl end-capping of graphene modification);

(6) Mix 100 parts by mass of modified polyurethane emulsion, 3 parts by mass of wetting and leveling agent Sliok-8858 and 2 parts by mass of hand feeling agent Sliok-3300, add 2 parts by mass of water-based polyurethane curing agent Perstorp WT2102, and stir for 30 Minutes later, a two-component water-based polyurethane leather finishing agent is obtained.

N,N-Dimethylformamide can dissolve the polymer polyurethane chain formed after the reaction is completed, reduce the viscosity of the product, and facilitate the neutralization agent triethylamine and the resin to be fully mixed for neutralization.

The performance test results of the waterborne polyurethane leather finishing agent prepared in this embodiment are shown in Table 1.

Example 2

(1) Add 6.6 parts by mass of polypropylene glycol (PPG1000) with a molecular weight of 1000 and 35.6 parts by mass of polycaprolactone diol (PCL2000) with a molecular weight of 2000 in the reaction vessel, dry it with a vacuum pump at 105°C for 30 minutes, and cool down to normal temperature Then add 35.7 parts by mass of isophorone diisocyanate and 0.05 parts by mass of catalyst dibutyltin dilaurate, and keep reacting at 80°C for 1 hour;

(2) Add 6.6 parts by mass of dimethylol butyric acid to the above reactant, raise the temperature to 80°C, and react for 2 hours; then add 8.9 parts by mass of 1,4-butanediol (dried and dehydrated in advance), and heat up to 80°C Polymerize for 3.5 hours, then lower the temperature to 42°C, add 5 parts by mass of triethylamine and 8 parts by mass of N,N-dimethylformamide that has been dehydrated in advance for neutralization, and the reaction time is 25 minutes to obtain a polyurethane prepolymer body;

(4) under the rotating speed of disperser 1000r/min, slowly add the deionized level of 200 mass parts in the polyurethane prepolymer, then raise the rotating speed to 3000r/min, emulsify 20min, obtain the waterborne polyurethane emulsion ( Hydroxyl-terminated water-based polyurethane emulsion with blue light);

(5) Put 1 mass part of graphene in 100 mass parts of deionized water, drop 1 mass part of silane coupling agent (KH-164, Guangzhou Longkai Chemical Industry), and ultrasonically disperse for 45min to obtain a stable dispersed graphene dispersion Liquid; Graphene dispersion liquid is mixed with the polyurethane emulsion that contains hydroxyl end-blocking under the disperser effect of 400r/min, obtains modified polyurethane emulsion (the aqueous polyurethane emulsion containing hydroxyl end-capping of graphene modification);

(6) Mix 100 parts by mass of modified polyurethane emulsion, 3 parts by mass of wetting and leveling agent Sliok-8858 and 2 parts by mass of hand feeling agent Sliok-3300, add 2 parts by mass of water-based polyurethane curing agent Perstorp WT2102, and stir for 30 Minutes later, a two-component water-based polyurethane leather finishing agent is obtained. The performance test results of the waterborne polyurethane leather finishing agent prepared in this embodiment are shown in Table 1.

Example 3

(1) Add 6.5 parts by mass of polypropylene glycol (PPG1000) with a molecular weight of 1000 and 35.1 parts by mass of polycaprolactone diol (PCL2000) with a molecular weight of 2000 in the reaction vessel, dry it with a vacuum pump at 105°C for 30 minutes, and cool down to normal temperature Then add 36.9 parts by mass of isophorone diisocyanate and 0.05 parts by mass of catalyst dibutyltin dilaurate, and keep reacting at 80°C for 1 hour;

(2) Add 6.5 parts by mass of dimethylol butyric acid to the above reactant, heat up to 80°C, and react for 2 hours; then add 8.8 parts by mass of 1,4-butanediol (dried and dehydrated in advance) and 1.4 parts by mass Trimethylolpropane, polymerized at 80°C for 3.5 hours, then lowered the temperature to 42°C, added 4.9 parts by mass of triethylamine and 8 parts by mass of N,N-dimethylformamide that had been dehydrated beforehand, and the reaction time Be 25 minutes, make polyurethane prepolymer;

(4) under the rotating speed of disperser 1000r/min, slowly add the deionized level of 200 mass parts in the polyurethane prepolymer, then raise the rotating speed to 3000r/min, emulsify 20min, obtain the waterborne polyurethane emulsion ( Hydroxyl-terminated water-based polyurethane emulsion with blue light);

(5) Place 1 mass part of graphene in 100 mass parts of deionized water, drop 1 mass part of silane coupling agent (KH-164), and ultrasonically disperse for 45min to obtain a stably dispersed graphene dispersion; disperse the graphene Liquid and the polyurethane emulsion containing hydroxyl end-capping are mixed under the disperser effect of 400r/min, obtain modified polyurethane emulsion (the water-based polyurethane emulsion containing hydroxyl end-capping of graphene modification);

(6) Mix 100 parts by mass of modified polyurethane emulsion, 3 parts by mass of wetting and leveling agent Sliok-8858 and 2 parts by mass of hand feeling agent Sliok-3300, add 2 parts by mass of water-based polyurethane curing agent Perstorp WT2102, and stir for 30 Minutes later, a two-component water-based polyurethane leather finishing agent is obtained. The performance test results of the waterborne polyurethane leather finishing agent prepared in this embodiment are shown in Table 1.

Example 4

(1) Add 7.2 parts by mass of polycaprolactone diol (PCL1000) with a molecular weight of 1000 and 38.9 parts by mass of polycaprolactone diol (PCL2000) with a molecular weight of 2000 in the reaction vessel, and dry it with a vacuum pump at 105°C for 30 Minutes, after cooling to normal temperature, add 35.8 parts by mass of isophorone diisocyanate, 5.1 parts by mass of hexamethylene diisocyanate trimer and 0.05 parts by mass of catalyst dibutyltin dilaurate, and keep the reaction at 80°C for 1 hour;

(2) Add 5.1 parts by mass of dimethylolbutyric acid to the above reactant, raise the temperature to 80°C, and react for 2 hours; then add 9.2 parts by mass of 1,4-butanediol (dried and dehydrated in advance), Polymerize for 3.5 hours, then lower the temperature to 42°C, add 3.9 parts by mass of triethylamine and 8 parts by mass of N,N-dimethylformamide that has been dehydrated in advance for neutralization, and the reaction time is 25 minutes to obtain a polyurethane prepolymerized body;

(4) under the rotating speed of disperser 1000r/min, slowly add the deionized level of 200 mass parts in the polyurethane prepolymer, then raise the rotating speed to 3500r/min, emulsify 20min, obtain the waterborne polyurethane emulsion ( Hydroxyl-terminated water-based polyurethane emulsion with blue light);

(5) Place 1 mass part of graphene in 100 mass parts of deionized water, drop 1 mass part of silane coupling agent (KH-164), and ultrasonically disperse for 45min to obtain a stably dispersed graphene dispersion; disperse the graphene Liquid and the polyurethane emulsion containing hydroxyl end-capping are mixed under the disperser effect of 400r/min, obtain modified polyurethane emulsion (the water-based polyurethane emulsion containing hydroxyl end-capping of graphene modification);

(6) Mix 100 parts by mass of modified polyurethane emulsion, 3 parts by mass of wetting and leveling agent Sliok-8858 and 2 parts by mass of hand feeling agent Sliok-3300, add 2 parts by mass of water-based polyurethane curing agent Perstorp WT2102, and stir for 30 Minutes later, a two-component water-based polyurethane leather finishing agent is obtained. The performance test results of the waterborne polyurethane leather finishing agent prepared in this embodiment are shown in Table 1.

Example 5

(1) Add 8.3 parts by mass of polycaprolactone diol (PCL1000) with a molecular weight of 1000 and 40.4 parts by mass of polycaprolactone diol (PCL3000) with a molecular weight of 3000 in the reaction vessel, and dry it with a vacuum pump at 105°C for 30 Minutes, after cooling to normal temperature, add 29.4 parts by mass of isophorone diisocyanate and 0.05 parts by mass of catalyst dibutyltin dilaurate, keep at 80°C for 1 hour;

(2) Add 6.4 parts by mass of dimethylolpropionic acid to the above reactant, heat up to 80°C, and react for 2 hours; then add 8.7 parts by mass of 1,4-butanediol (dried and dehydrated in advance) and 1.8 parts by mass Trimethylolpropane, polymerized at 80°C for 3.5 hours, then lowered the temperature to 42°C, added 4.9 parts by mass of triethylamine and 8 parts by mass of N,N-dimethylformamide that had been dehydrated beforehand, and the reaction time Be 25 minutes, make polyurethane prepolymer;

(4) under the rotating speed of disperser 1000r/min, slowly add the deionized level of 200 mass parts in the polyurethane prepolymer, then raise the rotating speed to 3500r/min, emulsify 20min, obtain the waterborne polyurethane emulsion ( Hydroxyl-terminated water-based polyurethane emulsion with blue light);

(5) Place 1 mass part of graphene in 100 mass parts of deionized water, drop 1 mass part of silane coupling agent (KH-164), and ultrasonically disperse for 45min to obtain a stably dispersed graphene dispersion; disperse the graphene Liquid and the polyurethane emulsion containing hydroxyl end-capping are mixed under the disperser effect of 400r/min, obtain modified polyurethane emulsion (the water-based polyurethane emulsion containing hydroxyl end-capping of graphene modification);

(6) Mix 100 parts by mass of modified polyurethane emulsion, 3 parts by mass of wetting and leveling agent Sliok-8858 and 2 parts by mass of hand feeling agent Sliok-3300, add 2 parts by mass of water-based polyurethane curing agent Perstorp WT2102, and stir for 30 Minutes later, a two-component water-based polyurethane leather finishing agent is obtained. The performance test results of the waterborne polyurethane leather finishing agent prepared in this embodiment are shown in Table 1.

Performance Testing:

(1) Solid content test: take 2g (m ₀ ) of the hydroxyl-terminated aqueous polyurethane emulsion prepared in Examples 1-5, place it in a petri dish, bake it in an oven at 75°C for 24 hours, and weigh it, and record the mass as m ₁ . The solid content is calculated using the following formula:

Solid content (%)=(m ₁ /m ₀ )*100%.

(2) Water absorption test: take a latex film (modified polyurethane emulsion film-forming prepared by Examples 1 to 5) with a length and width of 2*2 cm and a mass of _ma , immerse in deionized water, and place it at room temperature for 48 hours Wipe off the surface moisture with absorbent paper and weigh it as m _b . The water absorption rate is calculated using the following formula:

Water absorption (%)=[(m _b -m _a )/m _a ]*100%.

(3) Adhesion test: Apply the finishing agents prepared in Examples 1 to 5 evenly on soft leather with a coating rod, dry at 105°C for 45 seconds, and use the cross-cut method to test according to GB/T 9286-1998 Coating adhesion.

(4) Storage stability test: the stability test of the emulsion (water-based polyurethane emulsion containing hydroxyl end-capping prepared in Examples 1 to 5) is carried out according to GB/T 6753.3-1986; the storage stability is simulated by centrifugal accelerated sedimentation experiment. Centrifuge the emulsion at 3000r/min for 15 minutes in the machine, if there is no sediment, it is recognized as having a storage period of more than 6 months.

(5) Acetone resistance test: the coating film (formed by the modified polyurethane emulsion prepared in Examples 1 to 5) is weighed M ₀ ; soaked in acetone for 24 hours, then taken out, wiped off the liquid on the surface, weighed M ₁ , and measured Weight change rate (%) after sample soaking=[(M ₀ -M ₁ )/M ₀ ]*100%.

(6) Elongation at break test: prepare a dumbbell-shaped coating film (the coating agent prepared in Examples 1 to 5 forms a film), according to GB/T508-1998, with a minimum force of 0.01N and a tensile rate of 300mm/min test.

The performance test results of water-based polyurethane emulsion and coating agent prepared in each embodiment are shown in Table 1.

Water-based polyurethane emulsion and coating agent performance test result prepared by the embodiment 1～5 of table 1:

The above several implementation cases are only several preferred implementation modes of the present invention, and the above content is for illustrating the basic principles of the present invention, so the present invention is not limited by the above embodiments. On the premise of the basic principles and scope of the present invention, there will be various changes and improvements, and these changes and improvements all fall within the scope of the claimed invention.

Claims (8)

1. A graphene-modified two-component waterborne polyurethane leather finishing agent is characterized in that: it is composed of two parts stored separately, and the first part and the second part are all counted in parts by mass; The first part includes the following components: The second part is curing agent; 5-15 parts of curing agent; The polyol is more than one of PCL1000, PCL2000, PCL3000, PPG400, PPG1000, PPG2000, PBA3000; The hydrophilic diol chain extender is more than one of dimethylol propionic acid or dimethylol butyric acid; The dihydric alcohol/trihydric alcohol chain extender is 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerol more than one of . 2. Graphene modified two-component waterborne polyurethane leather finishing agent according to claim 1, is characterized in that: described first part also comprises wetting and leveling agent and feel agent, and described wetting and leveling agent and feel agent The mass parts are: Wetting and leveling agent 3-15 parts Hand feeling agent 3-15 parts. 3. The graphene-modified two-component water-based polyurethane leather finishing agent according to claim 2, characterized in that: the first part also includes an organic solvent, and the organic solvent is N,N-dimethylformamide. 4. according to the described graphene modified two-component water-based polyurethane leather finishing agent of claim 1, it is characterized in that: described polyhydric alcohol is more than two kinds in PCL1000, PCL2000, PCL3000, PPG400, PPG1000, PPG2000, PBA3000; The diisocyanate is one or more of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, hexamethylene diisocyanate, and toluene diisocyanate. 5. according to the described graphene modified two-component waterborne polyurethane leather finishing agent of claim 1, it is characterized in that: described catalyst is dibutyltin dilaurate or stannous octoate; Described neutralizing agent is more than one in triethanolamine, triethylamine, sodium hydroxide; The wetting and leveling agent is more than one of Sliok-8333, Sliok-8858 or Sliok-8035; The hand feeling agent is more than one of Sliok-9151, Sliok-3300, and Sliok-9148; The curing agent is more than one of Perstorp WT2102 and XD803; The silane coupling agent is more than one of KH-560, KH-570 and KH-164. 6. according to the preparation method of the graphene-modified two-component waterborne polyurethane leather finishing agent described in any one of claim 1～5, it is characterized in that: comprise the following steps: (1) Vacuum dehydration of the polyol, and then react with the diisocyanate under the action of a part of the catalyst, the reaction temperature is 60-80°C, and the reaction time is 1-3 hours, to obtain the prepolymer; (2) Add hydrophilic diol chain extender to the prepolymer, keep warm for 1-3 hours, add diol/triol chain extender and remaining catalyst, heat up to 70-85°C, polymerize 2-4 hours, lower the temperature, add a neutralizer and an organic solvent for neutralization, and obtain a polyurethane prepolymer; (3) Under medium-speed stirring, water is added in the polyurethane prepolymer, and after the water is added, the rotation speed is increased, and emulsified to obtain a hydroxyl-terminated aqueous polyurethane emulsion; (4) Graphene is mixed with water, drips silane coupling agent, ultrasonic dispersion, obtains graphene dispersion liquid; Graphene dispersion liquid is mixed with the water-based polyurethane emulsion that contains hydroxyl termination, obtains the modified water-based polyurethane emulsion; (5) When in use, mix the modified water-based polyurethane emulsion with a wetting and leveling agent and a hand feeling agent evenly, and finally add a curing agent to obtain a water-based polyurethane leather finishing agent. 7. according to the preparation method of the described graphene modified two-component water-based polyurethane leather finishing agent of claim 6, it is characterized in that: the rotating speed of medium speed described in step (3) is 800-1200r/min; Rotating speed refers to that rotating speed is increased to 3000-4000r/min; The addition of described water is: the mass ratio of water and hydrophilic glycol chain extender is (150-350): (3-15); The emulsification time is 15-30min; The temperature of the heat preservation reaction in step (2) is 60-80° C.; the temperature of the cooling is 35-45° C., and the time of the neutralization reaction is 20-45 minutes. 8. according to the preparation method of the described graphene-modified two-component water-based polyurethane leather finishing agent of claim 6, it is characterized in that: the condition of vacuum dehydration described in step (1) is vacuum drying at 90-110 ℃ for 0.5- 1 hour, the part of catalyst is 30-70% of the total amount of catalyst; The consumption relation of Graphene described in step (4) and water is to add 1-15 mass parts Graphene in every 100 mass parts water; Disperse evenly at a speed of 1/min.