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CN111925643A - High-water-oxygen-barrier waterborne polyurethane, preparation method thereof and bi-component polyurethane adhesive - Google Patents

High-water-oxygen-barrier waterborne polyurethane, preparation method thereof and bi-component polyurethane adhesive Download PDF

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CN111925643A
CN111925643A CN202010833584.6A CN202010833584A CN111925643A CN 111925643 A CN111925643 A CN 111925643A CN 202010833584 A CN202010833584 A CN 202010833584A CN 111925643 A CN111925643 A CN 111925643A
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hydrotalcite
aqueous polyurethane
water
graphene
self
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CN111925643B (en
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张义
张俊学
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Shanghai Dm New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention provides high-water-oxygen-barrier waterborne polyurethane, a preparation method thereof and bi-component polyurethane adhesive. Firstly, carrying out intercalation modification on hydrotalcite by adopting an anionic surfactant, then adding graphite oxide for ultrasonic treatment to form two-dimensional nanosheets of graphene oxide and stripped hydrotalcite nanosheets, wherein the graphene oxide with a large number of oxygen-containing functional groups on the surface and the hydrotalcite nanosheets displaying positive electricity are self-assembled under the driving of electrostatic action to form a loose ordered composite structure, namely a graphene-hydrotalcite self-assembly body; and mixing the self-assembly body with the aqueous polyurethane dispersion to obtain the aqueous polyurethane dispersion with high water oxygen barrier property. The graphene-hydrotalcite self-assembly forms a complex and tortuous special diffusion and permeation preventing path, inhibits the invasion of water and oxygen, can effectively improve the water and oxygen barrier property, and can enable the aqueous polyurethane dispersion liquid to have good film forming and bonding properties.

Description

High-water-oxygen-barrier waterborne polyurethane, preparation method thereof and bi-component polyurethane adhesive
Technical Field
The invention relates to the field of colloid materials, and particularly relates to high-water-oxygen-barrier waterborne polyurethane, a preparation method thereof and a bi-component polyurethane adhesive.
Background
Two-component polyurethane adhesives generally consist of a curing agent component containing isocyanate functional groups and a main component containing hydroxyl or amine functional groups. Two-component polyurethane coatings can generally be divided into solvent-borne polyurethane coatings and waterborne polyurethane glues. The aqueous polyurethane glue, especially the bi-component aqueous polyurethane glue, not only has the special flexibility, the friction resistance, the low temperature resistance and the good film forming ability of polyurethane, but also has the advantages of extremely low VOC emission, environmental pollution reduction and wide application prospect by taking water as a dispersing agent. The waterborne polyurethane has good water dispersibility, and simultaneously, the waterborne polyurethane has higher water-oxygen permeability and lacks of sufficient water-oxygen barrier performance. Particularly, when the bonding surface is metal, the bonding substrate is easily corroded and rusted after water vapor enters, and particularly, when water vapor remains, even perforation occurs. It is difficult to achieve sufficient sealing and corrosion prevention effects on the bonding base material. Therefore, it is of great significance to improve the barrier property of the aqueous polyurethane.
Researchers graft different types of organic resins onto polyurethane, and the water and oxygen barrier performance is enhanced by changing the structure of a high molecular chain segment. The main grafting modification methods include organic fluorine modification and organic silicon modification. The modification of the organic fluorine easily enlarges the particle size of the emulsion, is easy to break and settle, and simultaneously reduces the bonding strength to a base material. Researchers also add inorganic nanofillers to waterborne polyurethanes, which, by virtue of their extremely small particle size, increase the compactness of the glue and improve barrier and permeability. However, in order to achieve the necessary water oxygen barrier properties, a large amount of inorganic nano-materials must be added, which causes demulsification and makes it difficult to form a stable aqueous polyurethane dispersion.
In addition, the two-dimensional layered material has a high length-diameter ratio and better water and oxygen barrier properties than nano materials, such as graphene, montmorillonite and the like. The graphene is a two-dimensional nano layered material with single atom thickness, has the characteristics of high strength, high conductivity, high specific surface area and the like, and can obviously improve the mechanical property, the thermal property and the dielectric property of the polymer matrix composite material. The graphene has a two-dimensional layered structure with a high specific surface area, and can theoretically isolate the invasion of water, oxygen and corrosive ions to a metal matrix to a great extent, so that the corrosion rate of a metal substrate is effectively slowed down. However, the surface state of graphene is very stable, and each single-layer graphene sheet is bound by strong interlayer van der waals force, so that the lipophilicity and the hydrophilicity of each single-layer graphene sheet are poor, the graphene sheet cannot be effectively compounded with a polymer matrix, an aggregate is easily formed in the polymer matrix, water and oxygen barrier cannot be effectively realized in practical application, and the adhesion and the mechanical properties of a polymer are influenced. The two-dimensional layered material to achieve high barrier properties requires exfoliation and dispersion into nanosheets, for example, exfoliation from graphite oxide to form graphene oxide. Such exfoliated nanoplatelets can only be present in dilute solutions. If the dilute solution is used as a filler and added into the aqueous polyurethane dispersion, the dispersion must be greatly diluted, and the film forming and bonding performance of the double-component aqueous polyurethane adhesive is further influenced.
Therefore, it is difficult to achieve both the improvement of the water oxygen barrier property, the stabilization of the aqueous polyurethane dispersion and the high substrate adhesive strength in the prior art.
Disclosure of Invention
In view of the above, the present invention aims to provide a high water oxygen barrier waterborne polyurethane, a preparation method thereof and a two-component polyurethane adhesive. The waterborne polyurethane with high water oxygen barrier property provided by the invention can effectively improve the water oxygen barrier property of the waterborne polyurethane, and simultaneously ensures good film forming property and cohesiveness.
The invention provides a preparation method of waterborne polyurethane with high water oxygen barrier property, which comprises the following steps:
a) reacting hydrotalcite with an anionic surfactant in water to obtain an organic intercalation modified hydrotalcite dispersion liquid;
b) mixing the organic intercalation modified hydrotalcite dispersion liquid with graphite oxide and carrying out ultrasonic treatment to obtain a graphene-hydrotalcite self-assembly;
c) and mixing the graphene-hydrotalcite self-assembly with the aqueous polyurethane dispersion to obtain the aqueous polyurethane with high water oxygen barrier property.
Preferably, the mass ratio of the hydrotalcite to the graphite oxide is (0.5-20) to 1.
Preferably, in the step a), the mass ratio of the hydrotalcite to the anionic surfactant is 1 to (0.1-2);
the mass ratio of the hydrotalcite to the water is 1: 10-100.
Preferably, in the step a), the anionic surfactant is selected from one or more of carboxylate surfactant, sulfonate surfactant and sulfate surfactant;
the reaction temperature is 70-100 ℃, and the reaction time is 1-24 h.
Preferably, in the step b), the power of the ultrasonic treatment is 300-1000W, the frequency is 15-25 KHz, and the time is 1-8 h.
Preferably, the step b), after the ultrasonic treatment, further comprises: and (4) solid-liquid separation.
Preferably, in step c):
the aqueous polyurethane dispersion is a hydroxyl-terminated aqueous polyurethane dispersion;
the mass ratio of the graphene-hydrotalcite self-assembly to polyurethane in the aqueous polyurethane dispersion is (0.01-0.05) to 1;
the mixing speed is 100-1000 rpm, and the mixing time is 10-120 min.
The invention also provides the waterborne polyurethane with high water oxygen barrier property prepared by the preparation method in the technical scheme.
The invention also provides a bi-component polyurethane adhesive, which comprises a component A and a component B;
the component A comprises the waterborne polyurethane with high water oxygen barrier property in the technical scheme;
the component B comprises a curing agent.
Preferably, the curing agent is one or more of an aliphatic diisocyanate polymer and an aliphatic diisocyanate prepolymer;
the equivalent ratio of NCO groups in the curing agent to hydroxyl groups in the aqueous polyurethane dispersion is (0.2-5) to 1.
Firstly, carrying out intercalation modification on hydrotalcite by adopting an anionic surfactant, then adding graphite oxide for ultrasonic treatment to form two-dimensional nanosheets of graphene oxide and stripped hydrotalcite nanosheets, wherein the graphene oxide with a large number of oxygen-containing functional groups on the surface and the hydrotalcite nanosheets displaying positive electricity are self-assembled under the driving of electrostatic action to form a loose ordered composite structure, namely a graphene-hydrotalcite self-assembly body; and mixing the self-assembly body with the aqueous polyurethane dispersion to obtain the aqueous polyurethane dispersion with high water oxygen barrier property. The graphene-hydrotalcite self-assembly forms a more complex and tortuous special diffusion and permeation preventing path, inhibits the invasion of water and oxygen, can effectively improve the water and oxygen barrier property, and can enable the aqueous polyurethane dispersion liquid to have good film forming and bonding properties.
Test results show that the aqueous polyurethane dispersion provided by the invention can enable the peel strength of an adhesive film to be more than 8.5N/cm and the water vapor transmittance to be 0.25g.cm-2.day-1Oxygen transmission rate of 0.2cm3.cm-2.day-1The following.
Detailed Description
The invention provides a preparation method of waterborne polyurethane with high water oxygen barrier property, which comprises the following steps:
a) reacting hydrotalcite with an anionic surfactant in water to obtain an organic intercalation modified hydrotalcite dispersion liquid;
b) mixing the organic intercalation modified hydrotalcite dispersion liquid with graphite oxide and carrying out ultrasonic treatment to obtain a graphene-hydrotalcite self-assembly;
c) and mixing the graphene-hydrotalcite self-assembly with the aqueous polyurethane dispersion to obtain the aqueous polyurethane with high water oxygen barrier property.
Firstly, carrying out intercalation modification on hydrotalcite by adopting an anionic surfactant, then adding graphite oxide for ultrasonic treatment to form two-dimensional nanosheets of graphene oxide and stripped hydrotalcite nanosheets, wherein the graphene oxide with a large number of oxygen-containing functional groups on the surface and the hydrotalcite nanosheets displaying positive electricity are self-assembled under the driving of electrostatic action to form a loose ordered composite structure, namely a graphene-hydrotalcite self-assembly body; and mixing the self-assembly body with the aqueous polyurethane dispersion to obtain the aqueous polyurethane dispersion with high water oxygen barrier property. The graphene-hydrotalcite self-assembly forms a more complex and tortuous special diffusion and permeation preventing path, inhibits the invasion of water and oxygen, can effectively improve the water and oxygen barrier property, and can enable the aqueous polyurethane dispersion liquid to have good film forming and bonding properties.
With respect to step a): reacting hydrotalcite with an anionic surfactant in water to obtain an organic intercalation modified hydrotalcite dispersion liquid.
In the invention, the hydrotalcite is an anionic two-dimensional layered material, the laminate is formed by two metal hydroxides with different valence states, and inorganic anions are arranged between the layers of the laminate and comprise CO3 2-、NO3 -Or Cl-. In the present invention, the hydrotalcite includes, but is not limited to, magnesium aluminum hydrotalcite, the anion between layers of which is CO3 2-. In the present invention, the source of the hydrotalcite is not particularly limited, and may be any commercially available hydrotalcite.
In the invention, the anionic surfactant is selected from one or more of carboxylate surfactant, sulfonate surfactant and sulfate surfactant. In some embodiments of the invention, the anionic surfactant is sodium dodecylbenzene sulfonate, sodium lauryl sulfate, or sodium stearate.
In the invention, the mass ratio of the hydrotalcite to the anionic surfactant is preferably 1 to (0.1-2); in some embodiments of the invention, the mass ratio is 1: 0.75, 1: 0.50, or 1: 1. In the invention, the mass ratio of the hydrotalcite to the water is preferably 1 to (10-100); in some embodiments of the invention, the mass ratio is 1: 25 or 1: 50.
In the invention, the reaction temperature is preferably 70-100 ℃; in some embodiments of the invention, the temperature is 70 ℃ or 90 ℃. The reaction time is preferably 1-24 h; in some embodiments of the invention, the time is 10h or 12 h. After the reaction, the dispersion liquid of the hydrotalcite modified by the organic intercalation is formed.
With respect to step b): and mixing the organic intercalation modified hydrotalcite dispersion liquid with graphite oxide and carrying out ultrasonic treatment to obtain the graphene-hydrotalcite self-assembly.
In the present invention, the source of the graphene oxide is not particularly limited, and the graphene oxide may be a general commercial product or may be prepared according to a conventional preparation method well known to those skilled in the art.
In the invention, when graphite oxide is added, the mass ratio of hydrotalcite to graphite oxide is preferably controlled to be (0.5-20): 1 based on the amount of hydrotalcite initially charged, and if the mass ratio is too low or too high, the two nano sheets ultrasonically peeled are difficult to participate in electrostatic assembly to form an electrostatic self-assembly body. In some embodiments of the invention, the mass ratio is 2: 1, 4: 1, 5: 1, or 10: 1.
In the invention, the power of ultrasonic treatment is preferably 300-1000W; in some embodiments of the invention, the power is 500W. The frequency of ultrasonic treatment is preferably 15-25 KHz; in some embodiments of the invention, the frequency is 20 KHz. The time of ultrasonic treatment is preferably 1-8 h; in some embodiments of the invention, the time is 4 hours.
According to the method, after ultrasonic treatment, graphite oxide is stripped into graphene oxide nanosheets, hydrotalcite is stripped into two-dimensional nanosheets, and graphene oxide with a large number of oxygen-containing functional groups on the surface and the hydrotalcite nanosheets displaying positive electricity are promoted to be driven by electrostatic action to be self-assembled to form a loose ordered composite structure, namely a graphene-hydrotalcite self-assembly body; most of the surfactant is separated after assembly, and a small amount of the surfactant is possibly attached to the surface of the hydrotalcite nanosheet. The loose self-assembly prevents the two-dimensional layered materials from stacking and agglomerating respectively, can be better dispersed in polyurethane, and the self-assembly forms a complex and tortuous special diffusion and permeation preventing path, so that the invasion of water and oxygen is inhibited, the water and oxygen barrier property can be effectively improved, and the aqueous polyurethane dispersion liquid has good film forming and bonding properties.
In the present invention, it is preferable to further perform solid-liquid separation after the ultrasonic treatment. The solid-liquid separation method is not particularly limited in the present invention, and may be a conventional method known to those skilled in the art, such as filtration. And filtering and separating water in the system and a surfactant dissolved in the water to obtain the graphene-hydrotalcite self-assembly.
With respect to step c): and mixing the graphene-hydrotalcite self-assembly with the aqueous polyurethane dispersion to obtain the aqueous polyurethane with high water oxygen barrier property.
The aqueous polyurethane dispersion refers to a dispersion formed by dispersing polyurethane particles in water. In the present invention, the particle size of the polyurethane particles is 100 to 400 nm. In the invention, the aqueous polyurethane dispersion is preferably hydroxyl-terminated aqueous polyurethane dispersion, the hydroxyl-terminated polyurethane can be used for better forming a two-component polyurethane adhesive, and if non-hydroxyl-terminated polyurethane is used, the mechanical property is insufficient and the bonding strength is insufficient. In the present invention, the solid content of the hydroxyl-terminated aqueous polyurethane dispersion is preferably 10 to 70 wt% (based on 100% by weight of the aqueous polyurethane dispersion), and the hydroxyl-terminated content is preferably 0.5 to 5.0% (based on 100% by weight of the aqueous polyurethane dispersion). The source of the hydroxyl-terminated polyurethane dispersion is not particularly limited in the present invention, and the hydroxyl-terminated polyurethane dispersion can be prepared by general commercial products or preparation methods well known to those skilled in the art; wherein, the preparation method can be as follows: the polyurethane generated by the reaction of the polyol and the aliphatic polyisocyanate under the action of the anionic stabilizer forms a dispersion in water. In some embodiments of the invention, the hydroxyl-terminated aqueous polyurethane dispersion is dispercoll u54 from kossi polymers, inc and/or DME56 from shangham new materials technology, inc.
In the invention, the mass ratio of the graphene-hydrotalcite self-assembly to the polyurethane in the aqueous polyurethane dispersion is preferably (0.01-0.05): 1.
In the present invention, the mixing is preferably stirring mixing. The stirring speed is preferably 100-1000 rpm, and the stirring time is preferably 10-120 min. After stirring and mixing, uniform high water oxygen barrier aqueous polyurethane-based dispersion liquid is obtained.
In the invention, the high-water oxygen barrier waterborne polyurethane can also comprise an auxiliary agent. The auxiliary agent is the conventional auxiliary agent type in the field, and can be one or more of wetting dispersant, substrate wetting agent, rheological auxiliary agent, plasticizer, leveling agent, defoaming agent and catalyst. The addition sequence of the auxiliary agent is not particularly limited, and the auxiliary agent can be added into the aqueous polyurethane dispersion before the graphene-hydrotalcite self-assembly is mixed with the aqueous polyurethane dispersion, or can be added after the graphene-hydrotalcite self-assembly is mixed with the aqueous polyurethane dispersion.
The invention also provides the waterborne polyurethane with high water oxygen barrier property prepared by the preparation method in the technical scheme. The waterborne polyurethane provided by the invention can effectively improve the water oxygen barrier property of the waterborne polyurethane, and simultaneously ensures good film forming property and cohesiveness.
The invention also provides a bi-component polyurethane adhesive, which comprises a component A and a component B; the component A comprises the waterborne polyurethane with high water oxygen barrier property in the technical scheme; the component B comprises a curing agent.
In the invention, the curing agent is preferably one or more of aliphatic diisocyanate polymer and aliphatic diisocyanate prepolymer. The aliphatic diisocyanate polymer/prepolymer is a mixture of self-polymers of aliphatic diisocyanates. The aliphatic diisocyanate is preferably one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and hydrogenated phenyl methane diisocyanate (H12 MDI). Among them, the multimer of IPDI is preferably IPDI trimer. In the invention, the aliphatic diisocyanate prepolymer is a polymer which is obtained by reacting aliphatic diisocyanate with polyol, takes polyurethane as a framework and is terminated by NCO groups; the number average molecular weight of the obtained polymer is preferably 1000 to 5000. Wherein, the polyol includes but is not limited to one or more of polyether polyol, polyester polyol, polycarbonate polyol and polyvinyl alcohol. The source of the aliphatic diisocyanate polymer/prepolymer is not particularly limited, and the aliphatic diisocyanate polymer/prepolymer can be a general commercial product. In some embodiments of the invention, the aliphatic diisocyanate polymer/prepolymer is one or more of Bayhydur2655 from Bayer, Bayhydur401-70, and DMH1 from Shanghainem New materials science and technology, Inc. The curing agent can be well cured with the waterborne polyurethane with high water oxygen barrier property to form an adhesive film, and the isocyanate can also act with hydroxyl and carboxyl on the surface of the graphene to play a role in enhancing.
In the present invention, the curing agent is preferably used in the following amount: the equivalent ratio of NCO groups in the curing agent to hydroxyl groups in the aqueous polyurethane dispersion is (0.2-5) to 1, and more preferably (1.2-2) to 1. The invention is not limited to the method for preparing the adhesive film by using the two-component polyurethane adhesive, and the adhesive film is prepared by a conventional method well known to those skilled in the art, such as mixing the high water oxygen barrier waterborne polyurethane with a curing agent, and coating the mixture on the surface of a substrate to form a film-shaped material. And curing at 10-150 ℃, preferably 50-100 ℃, for 5-24 min, thereby forming the high-barrier waterborne polyurethane adhesive film. The obtained adhesive film can effectively improve the water oxygen barrier property, thereby enhancing the corrosion resistance and having high bonding property to the base material.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1.1 preparation of Water-resistant polyurethane with high Water oxygen resistance
S1, adding magnesium aluminum hydrotalcite (2.0g) into water (50g), adding sodium dodecyl benzene sulfonate (1.5g), heating to 90 ℃, and reacting for 12h to form organic intercalated hydrotalcite dispersion liquid. Adding graphite oxide (0.2g), ultrasonically dispersing and stripping (500W, 20KHz and 4h) at room temperature, and filtering to obtain the graphene-hydrotalcite electrostatic self-assembly.
S2, adding the obtained graphene-hydrotalcite electrostatic self-assembly into 200g of hydroxyl-terminated aqueous polyurethane dispersion DME56 (Shanghaimem science and technology Co., Ltd., solid content of 50%) at 1200rpm, and continuously stirring for 60min to obtain a uniform aqueous polyurethane dispersion liquid.
1.2 preparation of the adhesive film
Bayhydur2655 curing agent (14g) was added to the aqueous polyurethane dispersion obtained, stirred for 5min and mixed well. Coating on the surface of an aluminum plate, and curing at 80 ℃ for 4h to form a glue film.
Example 2
1.1 preparation of Water-resistant polyurethane with high Water oxygen resistance
S1, adding magnesium aluminum hydrotalcite (2.0g) into water (50g), adding sodium dodecyl sulfate (1.0g), heating to 90 ℃, and reacting for 10 hours to form organic intercalated hydrotalcite dispersion liquid. Adding graphite oxide (0.4g), ultrasonically dispersing and stripping (500W, 20KHz and 4h) at room temperature, and filtering to obtain the graphene-hydrotalcite electrostatic self-assembly.
S2, adding the obtained graphene-hydrotalcite electrostatic self-assembly into 200g of hydroxyl-terminated aqueous polyurethane dispersion DispercollU54 at 1200rpm, and continuously stirring for 60min to obtain a uniform aqueous polyurethane dispersion liquid.
1.2 preparation of the adhesive film
Bayhydur2655 curing agent (14g) was added to the aqueous polyurethane dispersion obtained, stirred for 5min and mixed well. Coating on the surface of an aluminum plate, and curing at 80 ℃ for 4h to form a glue film.
Example 3
1.1 preparation of Water-resistant polyurethane with high Water oxygen resistance
S1, adding magnesium aluminum hydrotalcite (2.0g) into water (50g), adding sodium stearate (2.0g), heating to 70 ℃ and reacting for 10 hours to form organic intercalated hydrotalcite dispersion liquid. Adding graphite oxide (0.5g), ultrasonically dispersing and stripping (500W, 20KHz and 4h) at room temperature, and filtering to obtain the graphene-hydrotalcite electrostatic self-assembly.
S2, adding the obtained graphene-hydrotalcite electrostatic self-assembly into 200g of hydroxyl-terminated aqueous polyurethane dispersion DispercollU54 at 1200rpm, and continuously stirring for 60min to obtain a uniform aqueous polyurethane dispersion liquid.
1.2 preparation of the adhesive film
To the aqueous polyurethane dispersion obtained was added DMH1 curing agent (15g), stirred for 5min, and mixed well. Coating on the surface of an aluminum plate, and curing at 90 ℃ for 6h to form a glue film.
Example 4
1.1 preparation of Water-resistant polyurethane with high Water oxygen resistance
S1, adding magnesium aluminum hydrotalcite (1.0g) into water (50g), adding sodium dodecyl benzene sulfonate (1.5g), heating to 70 ℃ and reacting for 10 hours to form organic intercalated hydrotalcite dispersion liquid. Adding graphite oxide (0.5g), ultrasonically dispersing and stripping (500W, 20KHz and 4h) at room temperature, and filtering to obtain the graphene-hydrotalcite electrostatic self-assembly.
S2, adding the obtained graphene-hydrotalcite electrostatic self-assembly into 200g of hydroxyl-terminated aqueous polyurethane dispersion DispercollU54 at 1200rpm, and continuously stirring for 60min to obtain a uniform aqueous polyurethane dispersion liquid.
1.2 preparation of the adhesive film
Bayhydur401-70 curing agent (15g) is added into the obtained waterborne polyurethane dispersion liquid, stirred for 5min and mixed evenly. Coating on the surface of an aluminum plate, and curing at 90 ℃ for 6h to form a glue film.
Example 5
1.1 preparation of Water-resistant polyurethane with high Water oxygen resistance
S1, adding magnesium aluminum hydrotalcite (2.0g) into water (50g), adding sodium dodecyl benzene sulfonate (1.5g), heating to 70 ℃ and reacting for 10 hours to form organic intercalated hydrotalcite dispersion liquid. Adding graphite oxide (0.5g), ultrasonically dispersing and stripping (500W, 20KHz and 4h) at room temperature, and filtering to obtain the graphene-hydrotalcite electrostatic self-assembly.
S2, adding the obtained graphene-hydrotalcite electrostatic self-assembly into 200g of hydroxyl-terminated aqueous polyurethane dispersion DME56 (Shanghaimem science and technology Co., Ltd., solid content of 50%) at 1200rpm, and continuously stirring for 60min to obtain a uniform aqueous polyurethane dispersion liquid.
1.2 preparation of the adhesive film
To the aqueous polyurethane dispersion obtained was added DMH1 curing agent (10g), stirred for 5min, and mixed well. Coating on the surface of an aluminum plate, and curing at 90 ℃ for 6h to form a glue film.
Comparative example 1
1.1 preparation of waterborne polyurethane: the procedure is as in example 1, except that the graphite oxide is replaced by hydrotalcite (i.e. no graphite oxide is added).
S1, adding magnesium-aluminum hydrotalcite (2.2g) into water (50g), adding sodium dodecyl benzene sulfonate (1.5g), heating to 70 ℃, reacting for 10 hours to form hydrotalcite dispersion liquid modified by organic intercalation, and filtering to obtain hydrotalcite modified by organic intercalation.
S2, adding the obtained organic intercalation modified hydrotalcite into 200g of hydroxyl-terminated aqueous polyurethane dispersion DME56 (Shanghaidim science and technology Co., Ltd., solid content of 50%) at 1200rpm, and continuously stirring for 60min to obtain an aqueous polyurethane dispersion.
1.2 preparation of the adhesive film
Bayhydur2655 curing agent (14g) was added to the aqueous polyurethane dispersion obtained, stirred for 5min and mixed well. Coating on the surface of an aluminum plate, and curing at 90 ℃ for 6h to form a glue film.
Comparative example 2
1.1 preparation of waterborne polyurethane: the procedure is as in example 1, except that the hydrotalcite is replaced by graphite oxide (i.e. no hydrotalcite is added).
Graphite oxide (2.2g) was added to 200g of hydroxyl-terminated aqueous polyurethane dispersion DME56 (Shanghaimem science and technology Co., Ltd., solid content 50%) and stirring was continued at 1200rpm for 60min to obtain an aqueous polyurethane dispersion.
1.2 preparation of the adhesive film
Bayhydur2655 curing agent (14g) was added to the aqueous polyurethane dispersion obtained, stirred for 5min and mixed well. Coating on the surface of an aluminum plate, and curing at 90 ℃ for 6h to form a glue film.
Comparative example 3
1.1 preparation of waterborne polyurethane: the procedure is as in example 1, except that the graphite oxide and the hydrotalcite are not subjected to electrostatic self-assembly.
S1, adding magnesium-aluminum hydrotalcite (2.2g) into water (50g), adding sodium dodecyl benzene sulfonate (1.5g), heating to 70 ℃ for reaction for 10h to form organic intercalation modified hydrotalcite dispersion, ultrasonically dispersing and stripping (500W, 20KHz and 4h) at room temperature, and filtering to obtain stripped organic intercalation modified hydrotalcite.
S2, adding graphite oxide (0.2g) into water (50g), ultrasonically dispersing and stripping (500W, 20KHz and 4h) at room temperature, and filtering to obtain stripped graphene oxide.
S3, at 1200rpm, firstly adding the obtained peeled organic intercalation modified hydrotalcite into 200g of hydroxyl-terminated aqueous polyurethane dispersion DME56 (Shanghaimem science and technology Co., Ltd., solid content of 50%), continuously stirring for 30min, then adding graphene oxide, and continuously stirring for 30min to obtain the aqueous polyurethane dispersion.
1.2 preparation of the adhesive film
Bayhydur2655 curing agent (14g) was added to the aqueous polyurethane dispersion obtained, stirred for 5min and mixed well. Coating on the surface of an aluminum plate, and curing at 90 ℃ for 6h to form a glue film.
Example 6
The adhesive films (thickness of 200 μm) obtained in examples 1 to 5 and comparative examples 1 to 3 were tested for their properties, and the results are shown in Table 1. The water vapor transmission rate is tested according to ASTM F-1249, and the oxygen transmission rate is tested according to ASTM D-3985.
TABLE 1 film Properties of examples 1-5 and comparative examples 1-3
Figure BDA0002638876590000111
As can be seen from the test results in Table 1, the adhesive films obtained in comparative examples 1 to 3 had peel strengths of 8N/cm or less and water vapor transmittances of 0.85g.cm-2.day-1Above, oxygen transmission rate of 0.75cm3.cm-2.day-1The above; the adhesive films obtained in the embodiments 1 to 5 of the invention have the peel strength of more than 8.5N/cm and the water vapor transmission rate of 0.25g.cm-2.day-1Oxygen transmission rate of 0.2cm3.cm-2.day-1The following; the water-based polyurethane disclosed by the invention can obviously improve the water-oxygen barrier property and the adhesive property of an adhesive film.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of waterborne polyurethane with high water oxygen barrier property is characterized by comprising the following steps:
a) reacting hydrotalcite with an anionic surfactant in water to obtain an organic intercalation modified hydrotalcite dispersion liquid;
b) mixing the organic intercalation modified hydrotalcite dispersion liquid with graphite oxide and carrying out ultrasonic treatment to obtain a graphene-hydrotalcite self-assembly;
c) and mixing the graphene-hydrotalcite self-assembly with the aqueous polyurethane dispersion to obtain the aqueous polyurethane with high water oxygen barrier property.
2. The preparation method according to claim 1, wherein the mass ratio of the hydrotalcite to the graphite oxide is (0.5-20): 1.
3. The preparation method according to claim 1, wherein in the step a), the mass ratio of the hydrotalcite to the anionic surfactant is 1: 0.1-2;
the mass ratio of the hydrotalcite to the water is 1: 10-100.
4. The method for preparing the surfactant according to claim 1 or 3, wherein in the step a), the anionic surfactant is selected from one or more of carboxylate type surfactant, sulfonate type surfactant and sulfate type surfactant;
the reaction temperature is 70-100 ℃, and the reaction time is 1-24 h.
5. The preparation method of claim 1, wherein in the step b), the power of the ultrasonic treatment is 300-1000W, the frequency is 15-25 KHz, and the time is 1-8 h.
6. The method according to claim 1 or 5, wherein the step b), after the ultrasonic treatment, further comprises: and (4) solid-liquid separation.
7. The method of claim 1, wherein in step c):
the aqueous polyurethane dispersion is a hydroxyl-terminated aqueous polyurethane dispersion;
the mass ratio of the graphene-hydrotalcite self-assembly to polyurethane in the aqueous polyurethane dispersion is (0.01-0.05) to 1;
the mixing speed is 100-1000 rpm, and the mixing time is 10-120 min.
8. The high-water-oxygen-barrier waterborne polyurethane prepared by the preparation method of any one of claims 1 to 7.
9. The bi-component polyurethane adhesive is characterized by comprising a component A and a component B;
the A component comprises the high water oxygen barrier aqueous polyurethane of claim 8;
the component B comprises a curing agent.
10. The two-component polyurethane adhesive according to claim 9, wherein the curing agent is one or more of an aliphatic diisocyanate polymer and an aliphatic diisocyanate prepolymer;
the equivalent ratio of NCO groups in the curing agent to hydroxyl groups in the aqueous polyurethane dispersion is (0.2-5) to 1.
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