CN112280284A - Liquid metal composite material, preparation method, remodeling method and recovery method - Google Patents
Liquid metal composite material, preparation method, remodeling method and recovery method Download PDFInfo
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Abstract
The invention discloses a liquid metal composite material, a preparation method, a remodeling method and a recovery method thereof. The preparation method of the liquid metal composite material comprises the following steps: providing a dynamic cross-linked polymer prepolymer; and mixing the dynamic cross-linked polymer prepolymer, the curing agent and the liquid metal, and curing and forming to obtain the liquid metal composite material. The liquid metal composite material prepared by the method has the advantages that the liquid metal composite material is anisotropic/isotropic in conductivity, and micro-nano-level liquid metal in the liquid metal composite material is recycled.
Description
Technical Field
The invention relates to the technical field of liquid metal composite materials, in particular to a liquid metal composite material, a preparation method, a remodeling method and a recovery method thereof.
Background
The room temperature Liquid Metal (LM) has the advantages of good heat conduction and electric conductivity, low toxicity, low modulus and the like, and can show special electric, thermal and mechanical properties when combined with an elastomer. The novel multifunctional composite material has good application prospect in the field of flexible electronic materials.
Compared with a bulk liquid metal (large liquid drop or block) composite material, the micro-nano level liquid metal can endow the composite material with more excellent performance, but has larger limitation. Different from the characteristic of easy recovery of liquid metal of a body liquid metal composite material, the micro-nano level liquid metal composite material is not easy to recover due to small particle size and uniform dispersion, thereby causing the sharp increase of material cost. On the one hand, most liquid metal composites currently use covalent polymers (e.g., PDMS) as the substrate, and the liquid metal is more difficult to recover due to the stability of the covalent polymers. Thus causing material waste and environmental pollution. On the other hand, most of the liquid metal conductive composite materials do not have anisotropic properties, and research and preparation technologies in the direction are very few, so that the liquid metal conductive composite materials have great application limitations in the field of electronic packaging materials.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a liquid metal composite material, a preparation method, a remodeling method and a recovery method, and aims to solve the problem that the existing liquid metal composite material is difficult to recover and has no anisotropic property, so that the application is limited.
A method of preparing a liquid metal composite, comprising:
providing a dynamic cross-linked polymer prepolymer;
mixing the dynamic cross-linked polymer prepolymer, a curing agent and liquid metal micro-nano droplets, and curing and molding to obtain a liquid metal composite material;
the dynamic cross-linked polymer prepolymer is a prepolymer of a dynamic cross-linked polymer with dynamic bonds formed after curing, and the dynamic bonds have the characteristics of dissociation and re-bonding.
The preparation method of the liquid metal composite material comprises the following steps of: one or more of a furan ring-containing polyurethane prepolymer, a disulfide bond-containing polymer prepolymer, a dynamic ester bond-containing polymer prepolymer, a dynamic borate bond-containing polymer prepolymer and an imine bond-containing polymer prepolymer.
The preparation method of the liquid metal composite material comprises the following steps:
and adding polycaprolactone diol, 2, 5-furan dimethanol and hexamethylene diisocyanate into the first solvent for reaction to prepare the furan ring-containing polyurethane prepolymer.
The preparation method of the liquid metal composite material comprises the following steps: one of dichloromethane, trichloromethane, tetrahydrofuran, acetone, butanone, dioxane, N-dimethylformamide and N-dimethylacetamide.
The preparation method of the liquid metal composite material comprises the step of carrying out ultrasonic dispersion on liquid metal in a cell crusher to prepare liquid metal droplets.
The preparation method of the liquid metal composite material further comprises the following steps: mechanically training the liquid metal composite material to enable the liquid metal composite material to have anisotropic conductive properties or isotropic conductive properties;
the mechanical training includes: and (3) either tension release training or compression release training.
The liquid metal composite material is prepared by the preparation method of the liquid metal composite material.
A method of remolding a liquid metal composite, comprising:
remolding the liquid metal composite material by adopting a hot pressing method or remolding the liquid metal composite material by adopting a wet process;
the hot pressing method comprises the following steps: heating and pressurizing the liquid metal composite material to obtain a dissociated liquid metal composite material;
cooling the dissociated liquid metal composite material to obtain a remolded liquid metal composite material;
the wet process comprises the following steps: dissolving the liquid metal composite material in a second solvent to obtain a liquid metal composite material solution after first dissociation;
and removing the second solvent in the liquid metal composite material solution after the first dissociation to obtain the remolded liquid metal composite material.
The method for remodeling the liquid metal composite material, wherein the second solvent comprises: one or more of nitrogen-nitrogen dimethylformamide, nitrogen-methyl pyrrolidone, nitrogen-nitrogen dimethylacetamide, toluene and dimethyl sulfoxide.
A method for recycling a liquid metal composite, comprising:
dissolving the liquid metal composite material in a third solvent to obtain a liquid metal composite material solution after second dissociation;
and centrifuging and washing the liquid metal composite material solution after the second dissociation, and collecting to obtain the liquid metal.
Has the advantages that: the liquid metal composite material is obtained by mixing the dynamic cross-linked polymer prepolymer, the curing agent and the liquid metal micro-nano liquid drops, curing and forming, wherein the dynamic cross-linked polymer formed by curing the dynamic cross-linked polymer prepolymer contains dynamic bonds capable of being dissociated and bonded again, so that the prepared liquid metal composite material is endowed with the recoverable self-repairing property, and further the anisotropic/isotropic conductivity of the liquid metal composite material and the recovery of the micro-nano liquid metal in the liquid metal composite material are realized.
Drawings
FIG. 1 is a schematic diagram of the network structure and principle of the dynamically crosslinked polymer of the present invention.
Detailed Description
The invention provides a liquid metal composite material, a preparation method, a remodeling method and a recovery method, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a liquid metal composite material, which comprises the following steps:
s100, providing a dynamic cross-linked polymer prepolymer;
s200, mixing the dynamic cross-linked polymer prepolymer, the curing agent and the liquid metal micro-nano liquid drops, and curing and forming to obtain a liquid metal composite material;
the dynamic cross-linked polymer prepolymer is a dynamic cross-linked polymer prepolymer which forms dynamic bonds with dissociation and re-bonding after being cured.
In the preparation method of the liquid metal composite material, the dynamic cross-linked polymer prepolymer, the curing agent and the ultrasonically dispersed liquid metal micro-nano droplets are uniformly mixed and added into a mould, and the multifunctional liquid metal composite material based on dynamic keys can be obtained by curing and molding. The composite material prepared by the invention has the characteristics of excellent anisotropic/isotropic conductivity, recyclable raw materials (especially the property of independently recycling liquid metal) and excellent mechanical properties.
In S100, the dynamic cross-linked polymer prepolymer is a substance that can react with a curing agent or the like to synthesize a dynamic cross-linked polymer. Referring to fig. 1, the dynamic cross-linked polymer refers to a network structure formed by dynamic bonds (also referred to as dynamic cross-links) between molecular chains in the polymer, wherein the dynamic bonds are dissociated and bonded under specific conditions, for example, the dynamic bonds are dissociated at a high temperature and are re-bonded at a low temperature.
The dynamic bond in the dynamic cross-linked polymer can be a dynamic physical bond or a dynamic covalent bond. Specifically, the dynamic physical bond may be a Diels-Alder (DA, Diels-Alder) bond; the dynamic covalent bond may be a disulfide bond, a dynamic ester bond, a dynamic borate bond, an imine bond. That is, the dynamically crosslinked polymers are classified into two types, one is a thermoplastic polymer crosslinked by dynamic physical bonds, and the other is a polymer crosslinked by dynamic covalent crosslinking bonds. In one embodiment of the present invention, the dynamically crosslinked polymer prepolymer comprises: one or more of a furan ring-containing polyurethane prepolymer, a disulfide bond-containing polymer prepolymer, a dynamic ester bond-containing polymer prepolymer, a dynamic borate bond-containing polymer prepolymer and an imine bond-containing polymer prepolymer.
In one embodiment of the present invention, the furan ring-containing polyurethane prepolymer is prepared by a preparation method comprising:
adding polycaprolactone diol (PCL-diol), 2, 5-furandimethanol (Fu-diol) and Hexamethylene Diisocyanate (HDI) into a first solvent for reaction to prepare the furan ring-containing polyurethane prepolymer.
The furan ring-containing polyurethane prepolymer can form furan ring-containing polyurethane in the subsequent steps. In the furan ring-containing polyurethane, a furan ring is positioned on a polyurethane main chain, and the furan ring on the main chain forms a DA bond.
The polycaprolactone diol, the 2, 5-furan dimethanol and the hexamethylene diisocyanate are monomers for synthesizing the polyurethane containing furan rings. The hexamethylene diisocyanate reacts with glycols to form polyurethane. The diol is polycaprolactone diol and 2, 5-furan dimethanol, so that furan groups are introduced into the main chain of the polyurethane.
The first solvent is used for dissolving the polycaprolactone diol, the 2, 5-furan dimethanol and the hexamethylene diisocyanate and forming a furan ring-containing polyurethane prepolymer solution. In one embodiment of the present invention, the first solvent includes: one of dichloromethane, trichloromethane, tetrahydrofuran, acetone, butanone, dioxane, N-dimethylformamide and N-dimethylacetamide.
Specifically, the S100 is prepared by using polycaprolactone diol, 2, 5-furandimethanol and hexamethylene diisocyanate as raw materials and synthesizing a polyurethane prepolymer (PU-Fu) with a furan ring in a main chain by a one-step method, wherein the molar ratio of the polycaprolactone diol to the 2, 5-furandimethanol is 1: (1-3) such as 1:2, the reaction temperature is room temperature or 20-80 ℃, such as 50 ℃, and the reaction time is 4-24 h, such as 8 h.
The liquid metal can be elemental metal, such as mercury, low-melting-point metal gallium, rubidium and cesium; or a mixed metal such as a mixed metal consisting of gallium, indium and tin.
The liquid metal droplets are micro-nano liquid metal droplets, have small particle size and can be uniformly dispersed in the polymer. In one embodiment of the present invention, the liquid metal droplets are prepared by ultrasonically dispersing liquid metal in a cell disruptor.
Specifically, in the process of preparing the liquid metal droplets by adopting a cell crusher, the ultrasonic time is 5-30 min, and the ultrasonic temperature is-15-0 ℃. The ultrasonic treatment time is 5-30 min, the particle size of liquid metal droplets can be adjusted, the particle size has an influence on the conductivity of the composite material, and the optimal ultrasonic treatment time is 10 min; the ultrasound time is 0 ℃ because the liquid metal is most stable at this temperature and the liquid metal reacts with oxygen in the air at too high a temperature, but it may be below 0 ℃ up to the freezing point of the liquid metal (-15 ℃), and the preferred temperature is 0 ℃.
200 is to crosslink and solidify the dynamic crosslinking polymer prepolymer in S100, and disperse liquid metal droplets in the formed dynamic crosslinking polymer.
In one embodiment of the present invention, the curing agent may also be referred to as a cross-linking agent, which allows the dynamic cross-linked polymer prepolymer to form a dynamic cross-linked polymer network. For the preparation of furan ring-containing polyurethane prepolymers, the crosslinker may be 4, 4' -Bismaleimidodiphenylmethane (BMI).
In the liquid metal composite material, the mass percentage of the liquid metal is not suitable to be too low or too high. If the mass percentage of the liquid metal is too low, the liquid metal composite material cannot form a conductive path and cannot conduct electricity; if the mass percentage of the liquid metal is too high, the mechanical properties of the liquid metal composite material are too poor. In one embodiment of the present invention, the liquid metal composite material contains 60 to 85 wt% of the liquid metal.
Specifically, S200 includes:
s201, fully mixing the liquid metal droplets with the dynamic cross-linked polymer prepolymer solution obtained in the step S100 and a cross-linking agent, and removing a first solvent through a rotary evaporator to obtain a viscous mixture to be cross-linked;
s202, pouring the viscous mixture into a mold, and curing for a period of time (for example, 48 hours) at a certain temperature (for example, 60-80 ℃) to obtain the liquid metal micro-nano composite material.
The liquid metal composite material obtained through the above S200 in the present invention is not electrically conductive in an initial stage, and the liquid metal composite material may change the material from an insulator to a conductor by means of mechanical training. In one embodiment of the present invention, the method further comprises:
s300, mechanically training the liquid metal composite material to enable the liquid metal composite material to have anisotropic conductive property or isotropic conductive property; wherein the mechanical training comprises: and (3) either tension release training or compression release training.
And S300, converting the liquid metal composite material into the anisotropic/isotropic conductive composite material in a mechanical training mode. In particular, the different ways of mechanical training may result in liquid metal composites having isotropic or anisotropic conductive properties. For example, the material is trained in a manner of stretching and releasing in the horizontal direction of the composite material, and finally the isotropic conductive material can be obtained; when compression-release training is carried out by adopting pressure which is locally vertical to the horizontal direction of the material, the material has anisotropic conductive property, namely, the area which is trained by the pressure is conductive in the vertical direction, and the area which is trained by the pressure is insulated in the horizontal direction. The content of the liquid metal in the liquid metal composite material and the mechanical training mode (including strain, pressure and times of training) have an influence on the conductivity of the liquid metal composite material.
Specifically, the liquid metal composite material is a liquid metal-furan ring-containing polyurethane composite material, the thickness of the liquid metal-furan ring-containing polyurethane composite material is 0.5mm, and the conductivity (isotropy) of the liquid metal composite material after horizontal stretching and releasing training is shown in table 1.
TABLE 1 conductivity of liquid metal composites after horizontal stretch release training
Specifically, the liquid metal composite material was a liquid metal-furan ring-containing polyurethane composite material having a thickness of 0.1mm, and the conductivity (anisotropy, i.e., conductivity at only the trained site) after the compression release training in the vertical direction was as shown in table 2.
TABLE 2 conductivity of liquid metal composites after vertical compression release training
| Sample (liquid metal content) | Resistance (omega) |
| 70wt％ | 56.22 |
| 80wt％ | 3.36 |
| 85wt％ | 0.48 |
Further, the invention provides a liquid metal composite material, wherein the liquid metal composite material is prepared by the preparation method of the liquid metal composite material. It can be seen that the liquid metal composite comprises: a dynamically crosslinked polymer, a liquid metal dispersed in the dynamically crosslinked polymer. The dynamic cross-linked polymer is a polymer with a network structure, and dynamic bonds are contained in the polymer and are used for connecting molecular chains in the polymer. The dynamically crosslinked polymer serves as a substrate for the liquid metal composite and is therefore also referred to as a polymer substrate. The liquid metal can be micro-nano level liquid metal. The liquid metal composite can exhibit anisotropy or isotropy after being subjected to anisotropic mechanical training.
The liquid metal composite material prepared by the invention has the property of recoverability, because the polymer in the composite material adopts a cross-linked network formed by dynamic bonds, the dynamic bonds can be dissociated and re-bonded under specific conditions, and the property of recoverability and self-repair is endowed to the liquid metal composite material. For example, a Diels-Alder (DA) bond crosslinked polymer network is adopted as a substrate in the liquid metal-furan ring-containing polyurethane composite material, the DA bond can be dissociated at high temperature (110-140 ℃) and is bonded again at low temperature (less than 80 ℃), and the recyclable self-repairing property is endowed to the liquid metal-furan ring-containing polyurethane composite material. Optionally, the dissociation temperature of the DA bond is 120 ℃. Based on the above, the invention provides a liquid metal composite material remodeling method, which comprises the following steps:
s400, remolding the liquid metal composite material by adopting a hot pressing method or remolding the liquid metal composite material by adopting a wet process;
the hot pressing method comprises the following steps: s410, directly remolding and molding the liquid metal composite material under certain pressure and temperature conditions;
the S410 is specifically: s411, heating and pressurizing the liquid metal composite material to obtain a dissociated liquid metal composite material;
s412, cooling the dissociated liquid metal composite material to obtain a remolded liquid metal composite material; the wet process comprises the following steps: s420, dissolving the liquid metal composite material in a second solvent, removing the second solvent, and performing remolding molding on the liquid metal composite material.
The S420 includes: s421, dissolving the liquid metal composite material in a second solvent to obtain a liquid metal composite material solution after first dissociation;
s422, removing the second solvent in the liquid metal composite material solution after the first dissociation to obtain the remolded liquid metal composite material.
S400 is a remolding process of the liquid metal composite, which may also be referred to as a composite recycling process. The step S410 is remolding the liquid metal composite material by a hot pressing method, which may also be referred to as solvent-free recovery of the liquid metal composite material. S420 is a wet process for remolding the liquid metal composite, which may also be referred to as a solvent recovery liquid metal composite.
In one embodiment of the present invention, in the S410, the hot pressing process parameter is 1h at a pressure of 12MPa and a temperature of 120 ℃, and then 48h at a temperature of 65 ℃.
The liquid metal composite of the present invention is capable of dissociating in a second solvent. In one embodiment of the present invention, in step S420, the liquid metal composite is first dissolved in a second solvent (the temperature may be 120 ℃), and then the second solvent is removed again to mold again. In one embodiment of the present invention, the second solvent comprises: one or more of nitrogen-nitrogen dimethylformamide, nitrogen-methyl pyrrolidone, nitrogen-nitrogen dimethylacetamide, toluene and dimethyl sulfoxide.
Since the dynamic bonds can be completely dissociated, the dynamically crosslinked polymer network can be dissolved in a specific solvent under certain conditions, thereby providing assistance to the separation and subsequent recovery of the liquid metal from the polymeric material. Based on this, the invention provides a liquid metal composite material recovery method, which comprises the following steps:
s500, dissolving the liquid metal composite material in a third solvent, centrifuging and washing, and collecting to obtain liquid metal droplets.
Specifically, the S500 includes:
s501, dissolving the liquid metal composite material in a third solvent to obtain a liquid metal composite material solution after second dissociation;
s502, centrifuging and washing the liquid metal composite material solution after the second dissociation, and collecting to obtain liquid metal droplets.
The S500 further comprises collecting polymeric material comprising:
s501, firstly dissolving the liquid metal composite material in a third solvent to obtain a second dissociated liquid metal composite material solution;
s502, centrifuging the liquid metal composite material solution after the second dissociation, washing the liquid metal composite material solution by using a solvent for multiple times to remove free polymer molecules, collecting the solvent, concentrating to obtain a polymer material, and collecting precipitates to obtain liquid metal droplets;
s503, placing the collected liquid metal drops into sodium hydroxide/diluted hydrochloric acid, grinding the liquid metal drops by adopting a mortar to remove a small amount of polymer molecules on the surfaces of the liquid drops, fusing the metal drops with each other to form large liquid metal drops, and washing the liquid metal drops for multiple times by using deionized water to recover the liquid metal.
Tests have shown that the liquid metal recovery rate can generally reach above 85%, wherein the number of washings and the degree of grinding affect the liquid metal recovery efficiency.
The liquid metal composite material of the present invention is capable of dissociating in a third solvent. Alternatively, the third solvent may be one or more of nitrogen-nitrogen dimethylformamide, nitrogen-methyl pyrrolidone, nitrogen-nitrogen dimethylacetamide, toluene, and dimethyl sulfoxide. That is, the material composition of the first dissociated liquid metal composite solution and the second dissociated liquid metal composite solution may be the same.
In summary, 1) the liquid metal composite material prepared by the present invention has a recyclable property, which not only means that the liquid metal composite material can be recycled (remolded), but also the polymer substrate (dynamic cross-linked polymer) and the nano liquid metal droplets can be respectively and independently recycled; 2) the micro-nano liquid metal composite material prepared by the invention has the mechanical training property, and can be trained into an isotropic or anisotropic conductor; 3) the micro-nano liquid metal composite material obtained by the invention has excellent mechanical properties; 4) the polymer substrate synthesized by the method has the characteristics of novel structure, excellent mechanical property and excellent self-repairing property.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing a liquid metal composite, comprising:
providing a dynamic cross-linked polymer prepolymer;
mixing the dynamic cross-linked polymer prepolymer, a curing agent and liquid metal, and curing and molding to obtain a liquid metal composite material;
the dynamic cross-linked polymer prepolymer is a prepolymer of a dynamic cross-linked polymer with dynamic bonds formed after curing, and the dynamic bonds have the characteristics of dissociation and re-bonding.
2. The method of claim 1, wherein the dynamic cross-linked polymer prepolymer comprises: one or more of a furan ring-containing polyurethane prepolymer, a disulfide bond-containing polymer prepolymer, a dynamic ester bond-containing polymer prepolymer, a dynamic borate bond-containing polymer prepolymer and an imine bond-containing polymer prepolymer.
3. The method for preparing a liquid metal composite material according to claim 2, wherein the furan ring-containing polyurethane prepolymer is prepared by a preparation method comprising:
and adding polycaprolactone diol, 2, 5-furan dimethanol and hexamethylene diisocyanate into the first solvent for reaction to prepare the furan ring-containing polyurethane prepolymer.
4. A method of producing a liquid metal composite according to claim 3, wherein the first solvent comprises: one of dichloromethane, trichloromethane, tetrahydrofuran, acetone, butanone, dioxane, N-dimethylformamide and N-dimethylacetamide.
5. The method for preparing a liquid metal composite material according to claim 1, wherein the liquid metal is micro-nano liquid metal formed by ultrasonic dispersion of a cell crusher.
6. A method of making a liquid metal composite as claimed in claim 1 further comprising: mechanically training the liquid metal composite material to enable the liquid metal composite material to have anisotropic conductive properties or isotropic conductive properties;
the mechanical training includes: and (3) either tension release training or compression release training.
7. A liquid metal composite material, which is prepared by the method for preparing the liquid metal composite material as claimed in any one of claims 1 to 6.
8. A method of remolding a liquid metal composite, comprising:
remolding the liquid metal composite material according to claim 7 by hot pressing or remolding the liquid metal composite material according to claim 7 by a wet process;
the hot pressing method comprises the following steps: heating and pressurizing the liquid metal composite material to obtain a dissociated liquid metal composite material;
cooling the dissociated liquid metal composite material to obtain a remolded liquid metal composite material;
the wet process comprises the following steps: dissolving the liquid metal composite material in a second solvent to obtain a liquid metal composite material solution after first dissociation;
and removing the second solvent in the liquid metal composite material solution after the first dissociation to obtain the remolded liquid metal composite material.
9. A liquid metal composite remolding method according to claim 8, wherein the second solvent includes: one or more of nitrogen-nitrogen dimethylformamide, nitrogen-methyl pyrrolidone, nitrogen-nitrogen dimethylacetamide, toluene and dimethyl sulfoxide.
10. A method of recycling a liquid metal composite, comprising:
dissolving the liquid metal composite of claim 7 in a third solvent to obtain a second dissociated liquid metal composite solution;
and centrifuging and washing the liquid metal composite material solution after the second dissociation, and collecting to obtain the liquid metal.
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| WO2022235211A1 (en) * | 2021-05-03 | 2022-11-10 | Nanyang Technological University | Flexible effective heat transport composites for thermal interface applications |
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