1. A sub-nanowire adhesive for use in a low temperature environment or an aqueous environment, comprising: 0.8-1.2 nm of inorganic sub-nanowires and organic solvent, and no other viscous additives.

2. The nanowire adhesive of claim 1, wherein the inorganic nanowires comprise at least one member selected from the group consisting of gadolinium oxyhydroxide nanowires, nickel molybdate nanowires, hydroxyapatite nanowires, tungsten oxide nanowires, vanadium phosphate nanowires, iron phosphomolybdate, zirconium phosphomolybdate, titanium phosphomolybdate, cerium phosphomolybdate, ytterbium phosphomolybdate, yttrium phosphomolybdate, manganese phosphomolybdate, cobalt phosphomolybdate, nickel phosphomolybdate, iron silicotungstate, bismuth phosphomolybdate, calcium phosphotungstate, and strontium phosphotungstate nanowires.

3. The nanowire adhesive of claim 1, wherein the inorganic nanowires are inorganic nanowires with surface ligands; and/or the organic solvent is a polar solvent and/or a non-polar solvent and/or a weak-polar solvent which are residual in a centrifugal mode in the process of preparing or recovering the inorganic sub-nanowires in the adhesive, the polarity of the weak-polar solvent is smaller than that of chloroform, the polarity of the polar solvent is not smaller than that of ethanol,

optionally, the surface ligands comprise at least one selected from oleylamine, oleic acid, n-octylamine, octadecylamine, oleyl alcohol.

4. The sub-nanowire adhesive as claimed in claim 1, wherein at least one of the following conditions is satisfied:

the solid content of the inorganic sub-nanowires in the adhesive is 60-80 wt%;

the applicable temperature of the adhesive is-196 ℃ to 190 ℃;

the viscosity of the adhesive is 100-10000 cps.

5. The sub-nanowire adhesive as claimed in claim 1, wherein the acting substrate of the adhesive comprises at least one selected from a metal material, a polymer material and an inorganic non-metal material;

optionally, the functional substrate of the adhesive comprises at least one selected from the group consisting of metal, plastic, paper, ceramic, and glass.

6. The sub-nanowire adhesive as claimed in claim 1, wherein at least one of the following conditions is satisfied:

the pH value of the water in the water-containing environment is 6-8.5;

the aqueous environment is formed from at least one selected from the group consisting of purified water, tap water, purified water, mineral water, deionized water, and seawater;

the low temperature environment comprises a freezing environment, a refrigerating environment or a cold chain transportation environment;

and the non-polar and/or weak-polar solvent and the polar solvent are adopted to realize the recovery and regeneration of the adhesive.

7. A method for preparing the sub-nanowire adhesive as claimed in any one of claims 1 to 6, wherein the method comprises scheme 1 or scheme 2:

scheme 1: (1) dissolving inorganic salt reaction raw materials in water, adding a ligand, and stirring at room temperature for reaction; (2) washing and centrifuging the solution obtained in the step (1) by adopting a non-polar and/or weak-polar solvent and a polar solvent so as to obtain an adhesive;

scheme 2: (i) dissolving inorganic salt reaction raw materials in water, and adding a ligand; (ii) (ii) placing the solution obtained in the step (i) in a high-pressure reaction kettle for solvothermal reaction; (iii) (iii) washing and centrifuging the solution obtained in step (ii) by using a non-polar and/or weakly polar solvent and a polar solvent so as to obtain the adhesive.

8. The method of claim 7, wherein at least one of the following conditions is satisfied:

the ligand is at least one selected from oleylamine, oleic acid, n-octylamine, octadecylamine and oleyl alcohol;

in the step (1), an organic solvent may be further added, wherein the organic solvent includes at least one selected from the group consisting of n-octane, cyclohexane, n-hexane, and octadecene;

in the step (i), an organic solvent may be further added, the organic solvent including at least one selected from the group consisting of n-octane, cyclohexane, n-hexane, and octadecene;

the nonpolar and/or weak polar solvent is at least one selected from cyclohexane, n-octane, n-hexane and toluene, and the polar solvent is ethanol and/or acetone;

the temperature of the solvothermal reaction is not more than 220 ℃.

9. Bonding use of the sub-nanowire adhesive of any one of claims 1 to 6 or the method of any one of claims 7 to 8 in low temperature and aqueous environments.

10. A label sticker is characterized by comprising label paper and an adhesive coated on the surface of the label paper, wherein the adhesive is the nanowire adhesive disclosed by any one of claims 1-6 or the nanowire adhesive prepared by the method disclosed by any one of claims 7-8.

Background

The adhesive refers to a material for bonding surfaces of homogeneous or heterogeneous objects together, and can be generally classified into inorganic adhesives and organic adhesives. The inorganic adhesive comprises cement, gypsum and the like, and the organic adhesive mainly refers to a high-molecular adhesive. Nowadays, the application of adhesives has penetrated into the aspects of people's life and engineering application. Along with the continuous improvement of the technology, the performance of the adhesive is gradually improved. Higher and higher requirements are put forward on different interfaces of different materials, use temperature, stability and the like. Although the adhesive used in people's life has high strength, the adhesive generally has irreversible property, such as large pollution to the adhesive surface, non-recyclable adhesive, and the like.

Disclosure of Invention

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a sub-nanowire adhesive, and a preparation method and application thereof. The adhesive is non-toxic and non-corrosive, high in bonding strength and stable in performance, can be suitable for various base materials, is wide in use temperature range, can show a long-term stable bonding effect in low-temperature and underwater environments, can also realize cyclic utilization, cannot cause bonding performance to be reduced or lost due to aging, cannot damage the bonding surface of the base material, can be widely applied to actual life, and is particularly suitable for the fields of cold chain transportation, seawater operation and the like.

The present invention is proposed based on the following findings of the inventors:

the problem that the label paper falls off due to the fact that the adhesive property of the label paper is reduced or loses efficacy in a low-temperature environment exists in the existing cold chain transportation process, products are mixed up if the label paper falls off, and a series of safety problems such as harm caused by difficulty in distinguishing medicines, blood or vaccines and the like can be caused if the label paper is not used; in addition, the existing adhesive can cause the reduction or the loss of the adhesive property due to aging or moisture influence and the like, especially underwater environment such as seawater environment. The inventors have surprisingly found that inorganic sub-nanowires (sub-nanowires refer to nanowire materials with a diameter close to the size of a single cell, and a length of up to several microns) can exhibit high viscosity in both frozen and/or neutral or near neutral underwater environments, the adhesive has long acting time, can not lose efficacy due to long-time low-temperature or underwater environment, can be suitable for bonding various base materials, the non-polar solvent/weak-polar solvent can be utilized to swell the inorganic sub-nanowire so as to realize the separation of the inorganic sub-nanowire and the bonding surface without damaging the bonding surface, then the adhesive is scraped off and added with the polar solvent for precipitation and recovery for repeated use, namely, the preparation of the adhesive by using the inorganic nanowires can realize the recycling of the adhesive, but the inorganic nanowire-based adhesive is difficult to keep stable viscosity in an underwater environment with excessive acidity and alkalinity; in addition, because the inorganic sub-nano wires have ultra-small diameter size, the specific surface area is quite high, the atom exposure ratio is close to 100%, the interaction with an external field is ultra-strong, and the foundation of the inorganic sub-nano wires serving as adhesives is laid.

To this end, according to a first aspect of the present invention, the present invention proposes a sub-nanowire adhesive for use in a low temperature environment or an aqueous environment. According to an embodiment of the invention, the adhesive comprises: 0.8-1.2 nm of inorganic sub-nanowires and organic solvent, and no other viscous additives. The inventor finds that the problem that the existing adhesive is poor in bonding effect in a freezing environment and a water-containing environment can be solved by preparing the adhesive based on the inorganic nanowires, the inorganic nanowires are independently adopted, uniform distribution and use of the inorganic nanowires on the surface of a base material are difficult to achieve, the inorganic nanowires are required to be uniformly dispersed in a solvent to form a semi-solid state, a better using effect can be achieved, and a long-term stable bonding effect can be achieved without adding other viscous additives. Compared with the prior art, the adhesive at least has the following advantages: 1. the adhesive has high bonding strength and stable performance, can show high viscosity in a freezing environment and/or a neutral or nearly neutral underwater environment, has long viscosity action time, cannot fail due to long-time low-temperature or underwater environment, cannot cause the reduction or loss of the bonding performance due to aging, and has the bonding strength of 1-20 MPa; 2. the paint is non-toxic and non-corrosive, can be suitable for various base materials, and has a wide range of use temperature; 3. the inorganic nanowire can be recycled, the bonding surface is not damaged after the inorganic nanowire is separated from the base material, specifically, the inorganic nanowire is swelled by utilizing a non-polar solvent and/or a weak-polar solvent to realize the separation of the inorganic nanowire from the base material, and the polar solvent is added to realize the precipitation recovery of the inorganic nanowire; 4. in the process of preparing the inorganic sub-nano wires and/or recovering the inorganic sub-nano wires in the adhesive, a small amount of residual polar solvent and/or non-polar solvent and/or weak polar solvent after centrifugation can be directly used as the adhesive without being dried and removed; 5. the method can be widely applied to actual life, and is particularly suitable for the fields of cold chain transportation, seawater operation and the like.

In addition, the sub-nanowire adhesive for low-temperature environment or water-containing environment according to the above embodiment of the present invention may further have the following additional technical features:

in some embodiments of the invention, the inorganic sub-nanowires comprise at least one selected from the group consisting of gadolinium oxyhydroxide sub-nanowires, nickel molybdate sub-nanowires, hydroxyapatite sub-nanowires, tungsten oxide sub-nanowires, vanadium phosphate sub-nanowires, iron phosphomolybdate, zirconium phosphomolybdate, titanium phosphomolybdate, cerium phosphomolybdate, ytterbium phosphomolybdate, yttrium phosphomolybdate, manganese phosphomolybdate, cobalt phosphomolybdate, nickel phosphomolybdate, iron silicotungstate, bismuth phosphomolybdate, calcium phosphotungstate, and strontium phosphotungstate sub-nanowires.

In some embodiments of the invention, the inorganic sub-nanowire is an inorganic sub-nanowire having a surface ligand; and/or the organic solvent is a polar solvent and/or a non-polar solvent and/or a weak-polar solvent which are/is centrifugally residual in the process of preparing or recovering the inorganic sub-nanowire in the adhesive, the polarity of the weak-polar solvent is less than that of chloroform, and the polarity of the polar solvent is not less than that of ethanol.

In some embodiments of the invention, the surface ligand comprises at least one selected from oleylamine, oleic acid, n-octylamine, octadecylamine, oleyl alcohol.

In some embodiments of the present invention, the sub-nanowire adhesive for use in a low temperature environment or an aqueous environment satisfies at least one of the following conditions: the solid content of the inorganic sub-nanowires in the adhesive is 60-80 wt%; the applicable temperature of the adhesive is-196 ℃ to 190 ℃; the viscosity of the adhesive is 100-10000 cps.

In some embodiments of the present invention, the action substrate of the adhesive comprises at least one selected from a metal material, a polymer material and an inorganic non-metal material.

In some embodiments of the present invention, the functional substrate of the adhesive comprises at least one selected from the group consisting of metal, plastic, paper, ceramic, and glass.

In some embodiments of the present invention, the sub-nanowire adhesive for use in a low temperature environment or an aqueous environment satisfies at least one of the following conditions: the pH value of the water in the water-containing environment is 6-8.5; the aqueous environment is formed from at least one selected from the group consisting of purified water, tap water, purified water, mineral water, deionized water, and seawater; the low temperature environment includes a freezing environment, a refrigeration environment, or a cold chain transportation environment.

In some embodiments of the present invention, the recovery and regeneration of the adhesive is achieved using non-polar and/or weakly polar solvents, polar solvents.

According to a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned sub-nanowire adhesive for a low-temperature environment or an aqueous environment. According to an embodiment of the invention, the method comprises scheme 1 or scheme 2:

scheme 1: (1) dissolving inorganic salt reaction raw materials in water, adding a ligand, and stirring at room temperature; (2) washing and centrifuging the solution obtained in the step (1) by adopting a non-polar and/or weak-polar solvent and a polar solvent so as to obtain an adhesive;

scheme 2: (i) dissolving inorganic salt reaction raw materials in water, and adding a ligand; (ii) (ii) placing the solution obtained in the step (i) in a high-pressure reaction kettle for solvothermal reaction; (iii) (iii) washing and centrifuging the solution obtained in step (ii) with a non-polar solvent and/or a weakly polar and polar solvent to obtain the adhesive.

The method for preparing the nanowire adhesive for the low-temperature environment or the water-containing environment in the embodiment of the invention is simple in process, and compared with the prior art, the prepared adhesive is non-toxic and non-corrosive, high in bonding strength and stable in performance, can be suitable for various base materials, is wide in use temperature range, can show a long-term stable bonding effect in the low-temperature and underwater environment, can realize recycling, cannot cause bonding performance reduction or loss due to aging, cannot damage the bonding surface of the base material, can be widely applied to actual life, and is particularly suitable for the fields of cold chain transportation, seawater operation and the like.

In some embodiments of the present invention, the method of preparing a sub-nanowire adhesive for use in a low temperature environment or an aqueous environment satisfies at least one of the following conditions: the ligand is at least one selected from oleylamine, oleic acid, n-octylamine, octadecylamine and oleyl alcohol; in the step (1), an organic solvent may be further added, wherein the organic solvent includes at least one selected from the group consisting of n-octane, cyclohexane, n-hexane, and octadecene; in the step (i), an organic solvent may be further added, the organic solvent including at least one selected from the group consisting of n-octane, cyclohexane, n-hexane, and octadecene; the non-polarity and/or weak polarity is at least one selected from cyclohexane, n-octane, n-hexane and toluene, and the polar solvent is ethanol and/or acetone; the temperature of the solvothermal reaction is not more than 220 ℃.

According to a third aspect of the present invention, the present invention proposes the bonding use of the above-mentioned sub-nanowire adhesive for a low-temperature environment or an aqueous environment and the method for preparing the sub-nanowire adhesive for a low-temperature environment or an aqueous environment in a low-temperature environment or an aqueous environment. The adhesive can effectively solve the problem that the adhesive performance of the existing adhesive is reduced or fails in low-temperature environments such as refrigeration or cold chain transportation and underwater environments.

According to a fourth aspect of the invention, a label sticker is presented. According to an embodiment of the invention, the label sticker comprises label paper and an adhesive coated on the surface of the label paper, wherein the adhesive is the nanowire adhesive used in a low-temperature environment or a water-containing environment or an adhesive obtained by the method for preparing the nanowire adhesive used in the low-temperature environment or the water-containing environment. Compared with the existing label sticker, the sticker has high bonding strength, stable bonding performance, no toxicity and no corrosiveness of the adhesive, can be suitable for various substrates, has a wide range of use temperature, can not be reduced or invalid even if being in a freezing environment for a long time, can not damage the bonding surface of the substrate when being separated from the substrate, and can effectively solve the problem that the existing label sticker is easy to fall off in a low-temperature environment.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

fig. 1 is a graph illustrating adhesion performance test of a sub-nanowire adhesive according to an embodiment of the present invention in different environments. Wherein, fig. 1a is a comparison graph of the bonding effect of the calcium tungstate sub-nanowire adhesive before and after being soaked in tap water for one month; FIG. 1b is a comparison graph of the bonding effect of the calcium tungstate sub-nanowire adhesive before and after being soaked in seawater for one month; FIG. 1c is a diagram showing the bonding effect of the strontium tungstate sub-nanowire adhesive after being stored for 24 hours at the liquid nitrogen temperature; FIG. 1d is a diagram showing the bonding effect of the strontium tungstate sub-nanowire adhesive after being stored at 180 ℃ for 24 hours; FIG. 1e is a diagram showing the bonding effect of the strontium tungstate sub-nanowire adhesive after bonding paper and a plastic plate for 24 hours at the liquid nitrogen temperature.

Fig. 2 is a flow diagram of a method of preparing a sub-nanowire adhesive, according to one embodiment of the present invention.

Fig. 3 is a flow diagram of a method of preparing a sub-nanowire adhesive according to still another embodiment of the present invention.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

According to a first aspect of the present invention, the present invention provides a sub-nanowire adhesive for use in a low temperature environment or an aqueous environment. According to an embodiment of the invention, the adhesive comprises: 0.8-1.2 nm of inorganic sub-nanowires and organic solvent, and no other viscous additives. The inventor finds that the problem that the existing adhesive is poor in bonding effect in a freezing environment and a water-containing environment can be solved by preparing the adhesive based on the inorganic sub-nanowires, the inorganic sub-nanowires are independently adopted, uniform distribution and use of the inorganic sub-nanowires on the surface of a base material are difficult to achieve, the inorganic sub-nanowires are required to be uniformly dispersed in a solvent to form a semi-solid state (in the process of preparing the inorganic sub-nanowires or recycling the inorganic sub-nanowires in the adhesive, a small amount of residual polar solvent and/or non-polar solvent and/or weak-polar solvent after centrifugation is not required to be dried and removed, and the solvent can be directly used), so that a better using effect can be achieved, and a long-term stable bonding effect can be achieved without adding other viscous additives. The adhesive has the following advantages: the adhesive has the advantages of no toxicity, no corrosion, high bonding strength, stable performance, suitability for various base materials, wide application temperature range, long-term stable bonding effect in low-temperature and underwater environments, cyclic utilization, no reduction or loss of bonding performance due to aging, no damage to the bonding surface of the base material, wide application in practical life, and particular suitability for the fields of cold chain transportation, seawater operation and the like.

The sub-nanowire adhesive for a low temperature environment or an aqueous environment according to the above embodiment of the present invention will be described in detail.

According to some embodiments of the present invention, the inventors found that, the types of inorganic nanowires in the nanowire adhesive are different, and the viscosity of the adhesive is also different, so that those skilled in the art can select the inorganic nanowires with suitable materials according to actual needs, for example, the inorganic sub-nanowire may include at least one selected from gadolinium oxyhydroxide sub-nanowire, nickel molybdate sub-nanowire, hydroxyapatite sub-nanowire, tungsten oxide sub-nanowire, vanadium phosphate sub-nanowire, iron phosphomolybdate, zirconium phosphomolybdate, titanium phosphomolybdate, cerium phosphomolybdate, ytterbium phosphomolybdate, yttrium phosphomolybdate, manganese phosphomolybdate, cobalt phosphomolybdate, nickel phosphomolybdate, iron silicotungstate, bismuth phosphomolybdate, calcium phosphotungstate, strontium phosphotungstate sub-nanowire, and other multi-acid sub-nanowires.

According to still some embodiments of the present invention, the inorganic nanowires in the nanowire adhesive may be nanowires having surface ligands, wherein the surface ligands used may be at least one selected from oleylamine, oleic acid, n-octylamine, octadecylamine, and oleyl alcohol, and the inventors have found that by using oleylamine, oleic acid, and the like as the surface ligands of the inorganic nanowires, the dispersibility of the inorganic nanowires in a solvent may be significantly improved, and the inorganic nanowires may be prevented from agglomerating in the solvent, so that the uniformity and stability of the adhesive may be significantly improved, and the adhesive effect of the nanowire adhesive may be further improved.

According to still other embodiments of the present invention, the organic solvent in the nanowire adhesive comprises a small amount of polar solvent and non-polar solvent and/or weakly polar solvent, and the inventors found that the inorganic nanowire is easily swelled in the non-polar solvent and/or weakly polar solvent, so that the bonding site of the inorganic nanowire and the substrate can be easily broken, the adhesive and the substrate can be separated, and then the polar solvent can be added to precipitate the adhesive, and the adhesive can be recycled and reused. Wherein the polar solvent can be ethanol and/or acetone, etc., and the nonpolar solvent and/or the weak polar solvent can be n-octane, cyclohexane, n-hexane, octadecene, etc.

According to still other embodiments of the present invention, the solid content of the inorganic nanowires in the adhesive may be 60 to 80 wt%, for example, 60 wt%, 62 wt%, 64 wt%, 66 wt%, 68 wt%, 70 wt%, 72 wt%, 74 wt%, 76 wt%, 78 wt%, or 80 wt%, and the like, after the adhesive is applied to a substrate, the organic solvent in the adhesive usually needs to be removed by drying or other methods, and what really has an adhesive effect is the inorganic nanowires, the inventors found that, if the solid content of the inorganic nanowires in the adhesive is too low, the amount of the adhesive needed is too much to achieve the desired adhesive effect, and is not favorable for rapid removal of the solvent; if the solid content of the inorganic nanowires in the adhesive is too high, the adhesive exists in a solid-like form, which is not beneficial to uniform dispersion of the inorganic nanowires on the surface of the base material, the consistency of the bonding strength of a bonding surface is difficult to maintain, and the bonding effect is influenced.

According to still other embodiments of the present invention, the applicable temperature of the adhesive is-196 ℃ to 190 ℃, and the inventors have verified through experiments that the adhesive based on inorganic nanowires of the present invention can be used not only in normal temperature and freezing environment, but also in ultra-low temperature environment as low as-196 ℃ and high temperature environment as high as 190 ℃ to maintain long-term stable bonding strength, for example, the adhesive can be used in stable environment as-196 ℃, 140 ℃, 90 ℃, 50 ℃, 20 ℃, 10 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 50 ℃, 80 ℃, 100 ℃, 150 ℃, 180 ℃ or 190 ℃ for a long time, and completely meet the use requirements of low temperature environment such as cold chain transportation, freezing and refrigeration, and normal temperature and high temperature environment.

According to still other embodiments of the present invention, the viscosity of the adhesive may be 100 to 10000cps, and the inventors have found that the types and solid contents of the inorganic sub-nanowires in the adhesive are different, and the viscosities of the inorganic sub-nanowires are also different, and the inventors have found that by selecting the inorganic sub-nanowires of different materials and controlling the solid contents of the adhesives, the viscosity of the adhesive can be changed within a range of 100 to 10000cps, for example, 200cps, 500cps, 800cps, 1000cps, 2000cps, 5000cps, 8000cps, 10000cps, etc., so that the viscosity can be flexibly selected according to different use requirements and application substrates, and the applicability of the adhesive can be greatly improved.

According to still other embodiments of the present invention, the action substrate based on inorganic nanowires in the present invention is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the action substrate can include at least one selected from metal materials, polymer materials and inorganic non-metal materials, and specifically can be pure metal, alloy, plastic, paper, ceramic, glass, and the like, so that the adhesion between metal and metal, metal and ceramic or glass, plastic and ceramic or glass, metal and paper, ceramic or glass and paper, ceramic and glass, and the like can be achieved, wherein the adhesion strength of the metal materials, polymer materials and inorganic non-metal materials using the nanowire adhesive in the present application can reach 1 to 20MPa, wherein it should be noted that the action substrate materials are different under the same adhesive area and amount, the bonding strength will vary accordingly.

According to still other embodiments of the present invention, the pH of water in an aqueous environment suitable for the sub-nanowire adhesive of the present invention may be 6 to 8.5, for example, 6.5 to 8.5, 6.8 to 7.2, 7 to 8, 7 to 7.8, 7.5 to 7.8, and the like, and the inventors found that the adhesive can exhibit high and long-term stable viscosity in a low-temperature environment and a neutral or near-neutral underwater environment, but cannot maintain stable viscosity if the acidity or alkalinity of water is too large, and the stability and reliability of the adhesive can be further ensured by using the adhesive in an aqueous environment with the pH in the above range. Specifically, the sub-nanowire adhesive can be used for bonding in water-containing environments or underwater environments such as purified water, tap water, purified water, mineral water, deionized water or seawater and the like, so as to ensure the reliability of the adhesive; in addition, the applicable stability of the nanowire adhesive can be as low as-196 ℃, and the bonding effect can be kept stable for a long time even in a low-temperature environment of liquid nitrogen, so that the low-temperature environment applicable to the nanowire adhesive is not particularly limited, and can be selected by a person skilled in the art according to actual needs, such as a freezing environment, a refrigerating environment or a cold chain transportation environment.

According to still other embodiments of the present invention, the recovery and regeneration of the adhesive can be achieved by using a non-polar and/or weakly polar solvent and a polar solvent, wherein the polarity of the weakly polar solvent is less than that of chloroform, and the polarity of the polar solvent is not less than that of ethanol, the inventors have found that the inorganic nanowires are easy to swell in the non-polar solvent and/or the weakly polar solvent, so that the bonding part of the inorganic nanowires and the substrate can be easily disconnected, the separation of the adhesive and the substrate can be achieved, the precipitation and recovery of the inorganic nanowires can be achieved by adding the polar solvent, therefore, when the separation of the adhesive and the substrate is desired, the bonding part of the substrate can be immersed in the non-polar solvent and/or the weakly polar solvent such as cyclohexane, n-octane, n-hexane, toluene, or the non-polar solvent and/or the weakly polar solvent such as cyclohexane, n-octane, n-hexane, toluene can be dropped to the bonding part of the substrate, the adhesive is swelled to easily break the bonding part, wherein the bonding agent can be completely scraped off by a medicine spoon or a scraper and placed in a centrifuge tube, a polar solvent such as ethanol or acetone is added to precipitate or centrifuge the bonding agent, and the obtained product can be continuously used as the adhesive to realize the recovery and the reutilization of the adhesive.

In summary, compared with the prior art, the nanowire adhesive for low-temperature environment or water-containing environment of the embodiment of the invention has at least the following advantages: 1. the adhesive has high bonding strength and stable performance, can show higher viscosity in a freezing environment and/or a neutral or nearly neutral underwater environment, has long viscosity action time, cannot be failed due to long-time low-temperature or underwater environment, and cannot cause the reduction or loss of the bonding performance due to aging; 2. the adhesive is non-toxic and non-corrosive, can be suitable for various base materials, and has a wide application temperature range, wherein the bonding strength of the adhesive can reach 1-20 MPa; 3. the inorganic nanowire can be recycled, the bonding surface is not damaged after the inorganic nanowire is separated from the base material, specifically, the inorganic nanowire is swelled by utilizing a nonpolar solvent and/or a solvent to realize the separation of the inorganic nanowire from the base material, and then the polar solvent is added to realize the precipitation recovery of the inorganic nanowire; 4. in the process of preparing the inorganic sub-nano wires and/or recovering the inorganic sub-nano wires in the adhesive, a small amount of residual polar solvent and/or non-polar solvent and/or weak polar solvent after centrifugation can be directly used as the adhesive without being dried and removed; 5. the method can be widely applied to actual life, and is particularly suitable for the fields of cold chain transportation, seawater operation and the like.

According to a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned sub-nanowire adhesive for a low-temperature environment or an aqueous environment. According to the embodiment of the invention, the preparation method can be carried out by adopting a room-temperature reaction method or a solvothermal reaction method, and the reaction temperature can be controlled to be 10-220 ℃. Specifically, the method comprises the following steps:

according to an embodiment of the present invention, when a room temperature reaction is adopted, it can be understood with reference to fig. 2 that inorganic salt reaction raw materials for forming inorganic nanowires may be dissolved in water, and a ligand is added, and the reaction is performed with continuous stirring at room temperature, and after the reaction is completed, the obtained reaction solution is washed and centrifuged using a non-polar or weakly-polar solvent and a polar solvent, so as to obtain inorganic nanowires, thereby obtaining an adhesive, wherein the inorganic nanowires may be dispersed in the polar solvent to obtain the adhesive. Further, before the reaction, a small molecule organic solvent can be added at the same time of adding the ligand, so that the inorganic nanowires obtained by the reaction can be more favorably and uniformly dispersed in the reaction liquid, wherein the small molecule organic solvent can be preferably at least one selected from the group consisting of n-octane, cyclohexane, n-hexane and octadecene.

According to the embodiment of the present invention, when the solvothermal method is adopted, it can be understood by referring to fig. 3 that inorganic salt reaction raw materials for forming inorganic nanowires can be dissolved in water, and a ligand is added, the mixed solution is placed in a high pressure reaction kettle after being uniformly stirred to perform solvothermal reaction, after the reaction is completed, the obtained reaction solution is washed and centrifuged by using a non-polar solvent and/or a weak polar solvent and a polar solvent, so as to obtain inorganic nanowires, thereby obtaining an adhesive, wherein the inorganic nanowires can be dispersed in the polar solvent to obtain the adhesive. Further, before the reaction, the ligand may be added simultaneously with the addition of the small-molecule organic solvent, which may preferably be at least one selected from the group consisting of n-octane, cyclohexane, n-hexane, and octadecene, thereby making it more advantageous to uniformly disperse the inorganic nanowires obtained by the reaction in the reaction solution.

According to some embodiments of the present invention, in preparing the nanowire adhesive, the ligand is added to significantly improve the dispersibility of the inorganic nanowires in a solvent, and avoid agglomeration of the inorganic nanowires in the solvent, so as to improve the uniformity and stability of the adhesive, wherein the ligand used may preferably be at least one selected from oleylamine, oleic acid, n-octylamine, octadecylamine, and oleyl alcohol.

According to still other embodiments of the present invention, the types of the polar solvent, the non-polar solvent and the weakly polar solvent used in the preparation of the nanowire adhesive in the present invention are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the polar solvent may be ethanol and/or acetone, and the non-polar solvent and/or the weakly polar solvent may be at least one selected from cyclohexane, n-octane, n-hexane and toluene.

In summary, the method for preparing the nanowire adhesive for the low-temperature environment or the water-containing environment according to the embodiment of the invention is simple in process, and compared with the prior art, the prepared adhesive is non-toxic and non-corrosive, high in bonding strength and stable in performance, can be applied to various base materials, is wide in use temperature range, can show a long-term stable bonding effect in the low-temperature and underwater environments, can realize recycling, cannot cause bonding performance reduction or loss due to aging, cannot cause damage to a bonding surface of the base material, can be widely applied to actual life, and is particularly suitable for the fields of cold chain transportation, seawater operation and the like. It should be noted that the features and effects described for the above-mentioned nanowire adhesive used in a low-temperature environment or an aqueous environment are also applicable to the method for preparing the nanowire adhesive used in a low-temperature environment or an aqueous environment, and are not repeated here.

According to a third aspect of the present invention, the present invention proposes the bonding use of the above-mentioned sub-nanowire adhesive for a low-temperature environment or an aqueous environment and the method for preparing the sub-nanowire adhesive for a low-temperature environment or an aqueous environment in a low-temperature environment or an aqueous environment. The adhesive can effectively solve the problem that the adhesive performance of the existing adhesive is reduced or fails in low-temperature environments such as refrigeration or cold chain transportation and underwater environments. It should be noted that the characteristics and effects described for the above-mentioned sub-nanowire adhesive used in a low-temperature environment or an aqueous environment and the preparation method thereof are also applicable to the application, and are not described in detail herein.

According to a fourth aspect of the invention, a label sticker is presented. According to an embodiment of the invention, the label sticker comprises label paper and an adhesive coated on the surface of the label paper, wherein the adhesive is the nanowire adhesive used in a low-temperature environment or a water-containing environment or an adhesive obtained by the method for preparing the nanowire adhesive used in the low-temperature environment or the water-containing environment. Compared with the existing label sticker, the sticker has high bonding strength, stable bonding performance, no toxicity and no corrosiveness of the adhesive, can be suitable for various substrates, has a wide range of use temperature, can not be reduced or invalid even if being in a freezing environment for a long time, can not damage the bonding surface of the substrate when being separated from the substrate, and can effectively solve the problem that the existing label sticker is easy to fall off in a low-temperature environment.

The label paper used in the label sticker of the present invention is not particularly limited, and those skilled in the art can select the label paper according to actual needs, for example, the label paper may be wood pulp paper, plastic paper, polymer film, composite paper of wood pulp paper and polymer film, single-layer paper or multi-layer paper; the use of the label paper is not particularly limited, and can be selected by those skilled in the art according to actual needs, and for example, the label paper can be used in a refrigerator, a freezer, or cold chain transportation, and specifically, can be used for storage or transportation of foods, drugs, blood plasma, vaccines, and the like. In addition, it should be noted that the characteristics and effects described for the above-mentioned sub-nanowire adhesive used in a low-temperature environment or a water-containing environment and the preparation method thereof are also applicable to the label sticker, and are not repeated here.

It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Example 1

1) Synthesis of bismuth phosphomolybdate sub-nanowires and obtaining of adhesives

Weighing 0.8g of phosphomolybdic acid and 0.2g of bismuth nitrate, adding the phosphomolybdic acid and the bismuth nitrate into a 40mL reaction kettle, adding 16mL of deionized water, and stirring for 10 minutes; then 10mL of octadecene and 6mL of oleylamine were added and stirred for 10 minutes. Subsequently, the reaction kettle is sealed and placed in an oven at 180 ℃ for 8 hours and then naturally cooled to room temperature. And pouring the product in the reaction kettle into a centrifuge tube, adding n-octane and ethanol, centrifuging and washing for three times to obtain the bismuth phosphomolybdate sub-nanowire, wherein the centrifuged product contains a small amount of n-octane and ethanol and is in a semisolid state, namely the bismuth phosphomolybdate sub-nanowire adhesive.

Example 2

1) Synthesizing calcium tungstate sub-nanowires and obtaining adhesive

Weighing 1g of phosphotungstic acid and 0.123g of calcium nitrate, adding into a 40mL reaction kettle, adding 16mL of deionized water, and stirring for 10 minutes; then 6mL oleylamine was added and stirred for 6 hours. And pouring the product in the reaction kettle into a centrifugal tube, adding n-octane and ethanol, and centrifuging and washing for three times to obtain the calcium tungstate sub-nanowire. The product obtained by centrifugation contains a small amount of n-octane and ethanol, and is in a semisolid state, namely the calcium tungstate sub-nanowire adhesive.

Example 3

1) Synthesizing strontium tungstate sub-nanowire and obtaining adhesive

Weighing 1g of phosphotungstic acid and 0.14g of strontium nitrate, adding into a 40mL reaction kettle, adding 16mL of deionized water, and stirring for 10 minutes; then 6mL oleylamine was added and stirred for 6 hours. And pouring the product in the reaction kettle into a centrifugal tube, adding n-octane and ethanol, and centrifuging and washing for three times to obtain the strontium tungstate nanowire. The product obtained by centrifugation contains a small amount of n-octane and ethanol, and is in a semi-solid state, namely the strontium tungstate sub-nanowire adhesive.

The performance of the sub-nanowire adhesives prepared in examples 2 and 3 was evaluated:

the general method comprises the following steps: preparing a base material such as a steel sheet, a glass sheet or a polyvinyl chloride sheet, uniformly coating the obtained adhesive on the base material such as a stainless steel sheet, a glass sheet or a polyvinyl chloride sheet by using a small spoon, pressing another sheet made of the same material on the sheet coated with the adhesive, pressing until no gap exists, and drying at room temperature or drying at 60 ℃.

The calcium tungstate sub-nanowire adhesive prepared in the embodiment 2 is used for bonding two pairs of small weights (the mass of each small weight is 10g, the bonding strength of the small weights is close to that of the small weights before and after soaking, the bonding strength is 4MPa), after bonding is completed, a large weight (the mass of each large weight is 500g) is hung below each pair of small weights, and a nylon rope is hung above each small weight to obtain two pairs of test samples. Two pairs of test specimens were placed in tap water and seawater, respectively, and suspended for one month. As can be seen from the comparison between the samples shown in fig. 1a and 1b before and after being soaked in water for one month, after being soaked for one month, the two pairs of small weights are still firmly bonded, and the bonding performance of the adhesive is stable. Although the sample soaked in the seawater is obviously rusted, the adhesive property of the adhesive is not affected.

Two pairs of small weights (the mass of each small weight is 10g) are bonded by adopting the strontium tungstate sub-nanowire adhesive prepared in the embodiment 3, after bonding is completed, a large weight (the mass of each large weight is 500g) is hung below each pair of small weights, and a metal wire is hung above each small weight to obtain two pairs of test samples. Two pairs of test samples were immersed in liquid nitrogen (-196 ℃) for 24 hours and stored at 180 ℃ for 24 hours, respectively. It can be seen from the pictures of the samples shown in fig. 1c and 1d after being stored at the liquid nitrogen temperature and the high temperature of 180 ℃, that the two pairs of small weights are still firmly bonded, and the bonding performance of the adhesive is stable.

The paper sheets are bonded on the plastic plate by adopting the strontium tungstate sub-nanowire adhesive prepared in the embodiment 3, and the plastic plate is kept at the temperature of liquid nitrogen (-196 ℃) for 24 hours, so that the bonding between the paper sheets and the plastic plate is still firm as shown in a test chart of fig. 1e after the two are bonded at the temperature of the liquid nitrogen, and the requirement of a cold chain transportation label can be completely met.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.