Super-hydrophilic polymer network composite material as well as preparation method and application thereof

Abstract

The invention provides a super-hydrophilic polymer network composite material as well as a preparation method and application thereof. The super-hydrophilic polymer network composite material comprises a polymer network substrate having a network structure formed by a polymer; the metal transition layer is arranged on the polymer net base material in a covering manner; the metal porous layer covers the metal transition layer and is provided with a micro-nano porous structure; and the hydrophilic polymer layer comprises a hydrophilic polymer filled in the metal porous layer. The multilayer reinforced super-hydrophilic polymer network composite material provided by the invention is high in porosity and good in hydrophilicity, has relatively high water storage capacity and capillary capacity, is suitable for preparing a vapor chamber wick and is suitable for being applied to the fields of oil-water separation and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials, and in particular relates to a super-hydrophilic polymer network composite material, a preparation method and application thereof, and a heat spreader. Background Art

[0002] Polymer mesh has the advantages of adjustable porosity, large specific surface area, and easy processing. It has great application potential as an adsorption material, filter material, heat dissipation material, etc. in sewage treatment, oil-water separation, and vapor chamber wicks. However, due to the poor hydrophilicity and insufficient capillary force of polymer mesh, its application effectiveness in certain fields is limited. For example, in application scenarios such as oil-water separation and vapor chamber wicks, good hydrophilicity and strong capillary force are one of the key performance indicators because they directly affect the transmission speed and efficiency of the liquid. The surface of the polymer mesh is highly hydrophobic and not easily wetted, which makes it difficult to selectively adsorb water in an oil-water mixture or quickly conduct liquid in a vapor chamber. Summary of the invention

[0003] In order to solve all or part of the above technical problems, the present invention provides the following technical solutions:

[0004] One of the purposes of the present invention is to provide a super hydrophilic polymer network composite material, comprising:

[0005] A polymer mesh substrate having a mesh structure formed of a polymer;

[0006] A metal transition layer is coated on the polymer mesh substrate;

[0007] A metal porous layer, which is coated on the metal transition layer and has a micro-nano porous structure;

[0008] The hydrophilic polymer layer comprises a hydrophilic polymer filled in the metal porous layer, wherein the hydrophilic polymer comprises one or a combination of polyvinyl alcohol, polyethylene glycol or polyvinyl pyrrolidone.

[0009] The super-hydrophilic polymer mesh composite material provided by the present invention has the advantages of high porosity and good hydrophilicity, and has good water storage capacity and capillary capacity; wherein the functional layers complement each other's advantages and are multifunctionally coupled to form a bottom-up multi-layer reinforced super-hydrophilic polymer mesh composite material, which can be used in the fields of heat spreader liquid wick, oil-water separation, etc.

[0010] In some embodiments, the micro-nano porous structure is a capillary structure, wherein 20-50% of the volume of the pores are macropores with a pore size of 30 μm to 300 μm, and 50-80% of the volume of the pores are small pores with a pore size of 100 nm to 1000 nm, wherein the pore size of the macropores increases in a direction away from the polymer mesh substrate. The capillary structure formed by the composite of macropores and small pores can increase the penetration speed of liquid into the structure and the transmission speed in the structure compared to a porous structure with a single pore size, thereby making the composite material of the present invention more hydrophilic.

[0011] Compared with hydrophilic composite materials with metal as the substrate, the polymer mesh substrate used in the present invention has good flexibility and good processability, making it more suitable for special-shaped heat spreaders, oil-water separation membranes, etc.

[0012] In some embodiments, the hydrophilic polymer is attached to the pore wall of the micro-nano porous structure, and forms a hydrophilic polymer layer with a thickness of 5 to 10% of the pore diameter on the pore wall. Compared with the situation where the hydrophilic polymer completely fills the pores, the present invention further controls the filling thickness of the hydrophilic polymer layer in the pores of the micro-nano porous structure, so that the micro-nano porous structure has a certain water storage space, so that the composite material provided by the present invention has both good water transmission performance and water storage capacity.

[0013] In some embodiments, the porosity of the metal porous layer is 20-90%.

[0014] In some embodiments, the thickness ratio of the polymer mesh substrate, the metal transition layer, and the metal porous layer is 1-100: 0.05-2: 1-100. Through systematic research, the present invention has found that when the thickness ratio of the polymer mesh substrate, the metal transition layer, and the metal porous layer is within this range, the composite material formed not only has good water storage capacity and capillary capacity, but also has good bonding between the layers, and the overall strength is suitable and not easy to deform. In particular, if the metal transition layer is thin, it will lead to uneven transition layer, and subsequent plating will not be deposited. If the thickness of the metal transition layer is large, it will lead to excessive plating stress, resulting in large deformation of the polymer mesh; if the thickness of the metal porous layer is low, the porous structure formed will be discontinuous. If the thickness of the metal porous layer is large, the strength of the porous plating formed will be low.

[0015] In some embodiments, the thickness of the polymer mesh substrate is 50N200 μm.

[0016] In some embodiments, the thickness of the metal transition layer is 0.5-50 μm.

[0017] In some embodiments, the thickness of the porous metal layer is 10-200 μm.

[0018] In some embodiments, the mesh number of the polymer mesh substrate is 120 to 500. The mesh number of the polymer mesh substrate has a certain influence on the water storage capacity and water permeability. If the mesh number is lower, the water storage capacity will be small and the capillary effect will be insufficient, which will affect the heat dissipation of the heat spreader. If the mesh number is higher, the water permeability will be low, which will affect the oil-water separation performance.

[0019] In some embodiments, the polymer mesh substrate is made of one or a combination of polypropylene, polyethylene or nylon.

[0020] In some embodiments, the metal transition layer is made of copper.

[0021] In some embodiments, the material of the metal porous layer includes copper.

[0022] In some preferred embodiments, the metal transition layer and the metal porous layer are both made of copper, which has good thermal conductivity and high deposition efficiency, and can form the copper layer of the micro-nano porous structure by electrodeposition.

[0023] In some embodiments, the thickness of the hydrophilic polymer layer is 1N10 μm.

[0024] In some embodiments, the contact angle between the super hydrophilic polymer network composite material and water is 0°.

[0025] A second object of the present invention is to provide a method for preparing a super-hydrophilic polymer network composite material, comprising:

[0026] At least one chemical plating method is used to form a metal transition layer on the surface of the polymer mesh substrate to obtain a first intermediate material;

[0027] At least using an electrodeposition method to deposit a second metal on the surface of the first intermediate material to form a metal porous layer having a micro-nano porous structure, thereby obtaining a second intermediate material;

[0028] The hydrophilic polymer is filled into the metal porous layer to obtain a super-hydrophilic polymer network composite material.

[0029] The present invention uses chemical-electrochemical technology to wrap the metal transition layer and the metal porous layer on the polymer mesh skeleton to improve its water storage capacity; and then constructs a hydrophilic polymer layer to further improve the hydrophilicity, water storage capacity and capillary capacity of the conforming material. Among them, a chemical plating method is first used to form a uniformly deposited metal transition layer on the surface of the polymer mesh. The metal transition layer as a transition layer can make the metal porous layer formed by subsequent electrodeposition well combined with it, solving the problem that direct electroplating on the surface of the polymer mesh substrate cannot form a metal porous layer with a porous structure; in addition, the metal porous layer is formed by an electrodeposition method, and the coating thickness and the pore size of the porous layer can be adjusted by adjusting the electrodeposition parameters, forming a micro-nano porous structure with large pores and small pores, and the pore size of the large pores increases in the direction away from the polymer mesh substrate.

[0030] In some embodiments, the chemical plating solution used in the chemical plating includes a soluble salt of a first metal, a complexing agent and a reducing agent, and the first metal correspondingly forms the metal transition layer.

[0031] In some embodiments, the process conditions of the chemical plating include: a plating temperature of 50 to 80° C. and a time of 5 to 120 min.

[0032] In some embodiments, the chemical plating solution includes 5-25 wt % of a soluble salt of a first metal, 2-60 wt % of a complexing agent, and 0.1-15 wt % of a reducing agent.

[0033] In some embodiments, the first metal includes copper, that is, the material of the formed metal transition layer includes copper, and the chemical plating solution includes one or more of copper sulfate, copper chloride or copper nitrate, but is not limited thereto.

[0034] In some embodiments, the complexing agent includes one or a combination of more than one of potassium sodium tartrate, disodium ethylenediaminetetraacetic acid, sodium sulfosalicylate or triethanolamine, but is not limited thereto.

[0035] In some embodiments, the reducing agent includes one or a combination of glyoxylic acid, formaldehyde or dimethylaminoborane, but is not limited thereto.

[0036] In some embodiments, the electroplating solution used in the electrodeposition includes a soluble salt of the second metal and an acid.

[0037] In some embodiments, the electrodeposition uses the first intermediate material as a cathode and the anode is made of phosphor copper.

[0038] In some embodiments, the electrodeposition process conditions include: a current density of 5 to 200 A / dm 2 , temperature is 30-40℃, time is 5-300s.

[0039] In some embodiments, the electroplating solution includes 2-20 wt % of a soluble salt of the second metal and 5-20 wt % of an acid.

[0040] In some embodiments, the second metal includes copper, that is, the material of the formed metal porous layer includes copper, and the electroplating solution includes one or a combination of copper sulfate and copper chloride, but is not limited thereto.

[0041] In some embodiments, the acid includes one or a combination of sulfuric acid and hydrochloric acid, but is not limited thereto.

[0042] In some embodiments, filling the hydrophilic polymer into the metal porous layer specifically includes: soaking the second intermediate material in a solution containing the hydrophilic polymer for 30 to 300 seconds, and drying to obtain the super hydrophilic polymer network composite material.

[0043] In some embodiments, the hydrophilic polymer includes one or a combination of polyvinyl alcohol, polyethylene glycol or polyvinyl pyrrolidone, but is not limited thereto.

[0044] In some embodiments, the solution containing the hydrophilic polymer includes 1-50 wt % of the hydrophilic polymer.

[0045] In some embodiments, the drying temperature is 30-60° C., and the drying time is 5-60 min.

[0046] In some embodiments, the preparation method further comprises pre-treating the polymer mesh substrate, and the pre-treatment comprises: alkali washing the polymer mesh substrate, for example, placing the polymer mesh substrate in a 30 wt % sodium hydroxide solution at 80° C. for 5 minutes for alkali washing to remove oil.

[0047] In a typical embodiment, the preparation method comprises the following steps:

[0048] The copper salt, the complexing agent and the reducing agent are mixed to obtain a chemical plating solution; the prepared chemical copper plating solution is placed in a constant temperature device, the plating temperature and time are controlled, and the polymer mesh is immersed in the chemical plating solution for plating to form a copper transition layer on the polymer mesh, that is, a first intermediate material is obtained; after the plating is completed, the first intermediate material is rinsed and dried;

[0049] The first intermediate material is used as a cathode, and the cathode and the anode are placed in a copper electroplating solution for an electrodeposition reaction to form a porous copper plating layer having a micro-nano porous structure on the copper plating layer to obtain a second intermediate material;

[0050] The hydrophilic polymer is filled into the second intermediate material to obtain a multi-layer reinforced super-hydrophilic polymer network composite material.

[0051] In a more specific typical embodiment, the preparation method comprises the following steps:

[0052] (1) immersing the pretreated polymer network in a chemical plating solution, and chemically depositing at 50-80° C. for 5-120 min to obtain a first intermediate material; the chemical plating solution comprises 5-25 wt % of a first metal soluble salt, 2-60 wt % of a complexing agent, and 0.1-15 wt % of a reducing agent;

[0053] (2) immersing the first intermediate material and the phosphor copper sheet in an electroplating solution to form an electrochemical working system with the first intermediate material as a cathode and the phosphor copper as an anode; connecting a power source and applying a current density of 5 to 200 A / dm between the anode and the cathode. 2 The electroplating solution comprises 2-20 wt % copper salt and 5-20 wt % acid;

[0054] (3) Immersing the second intermediate material in a solution containing a hydrophilic polymer, taking it out after soaking for 30 to 300 seconds, and drying it at 30 to 60° C. for 5 to 60 minutes to obtain a multi-layer reinforced super-hydrophilic polymer network composite material; the hydrophilic polymer includes any one of polyvinyl alcohol, polyethylene glycol, and polyvinyl pyrrolidone, or a combination of two or more thereof.

[0055] The third object of the present invention is to provide the use of the super-hydrophilic polymer net composite material described in any of the above technical solutions or the super-hydrophilic polymer net composite material prepared according to any of the methods described in the above technical solutions in the preparation of a vapor chamber wick or oil-water separation. The separation efficiency of oil-water separation using the composite material is above 99% and has a high flux.

[0056] The fourth object of the present invention is to provide a vapor chamber, in particular a special-shaped vapor chamber, comprising a shell and a liquid wick disposed inside the shell, wherein the liquid wick comprises a super-hydrophilic polymer mesh composite material as described in any of the above technical solutions or a super-hydrophilic polymer mesh composite material prepared according to any of the methods described. The temperature difference between any two points on the surface of the vapor chamber is small, and the temperature difference is below 3°C.

[0057] Compared with the prior art, the present invention has at least the following beneficial effects: the multi-layer reinforced super-hydrophilic polymer mesh composite material provided by the present invention has the advantages of high porosity and good hydrophilicity, and has good water storage capacity and capillary capacity; wherein the functional layers complement each other's advantages and are multifunctionally coupled to form a multi-layer reinforced super-hydrophilic polymer mesh material; the composite material is suitable for the fields of vapor chamber wicks, oil-water separation, etc., and the temperature difference between any two points on the surface of the vapor chamber prepared by using the composite material is small, and the oil-water separation by using the composite material has a higher flux and a higher separation efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0059] Figure 1 Schematic diagram of the structure of a super-hydrophilic polymer network composite material in one embodiment of the present invention;

[0060] Figure 2 is a SEM image of the super-hydrophilic polymer network composite material in Example 1 of the present invention;

[0061] Figure 3 This is a picture of the contact angle of water on the surface of the super-hydrophilic polymer network composite material in Example 1 of the present invention. DETAILED DESCRIPTION

[0062] The technical solution of the present invention is described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement the technical solution of the present invention. The specific functional details disclosed herein should not be interpreted as limiting, but only as the basis for the claims and as a representative basis for teaching those skilled in the art to adopt the present invention in different ways in any appropriate detailed embodiment.

[0063] Unless otherwise specified, the raw materials and reagents used in the specific embodiments of the present invention are all commercially available.

[0064] Example 1

[0065] This embodiment provides a super-hydrophilic polymer network composite material and a preparation method thereof, which specifically includes:

[0066] (1) pre-treating a 150-mesh polypropylene mesh, wherein the pre-treatment specifically comprises: immersing the polymer mesh in a 30 wt % sodium hydroxide solution at 80° C. for 5 minutes, and then ultrasonically cleaning it with deionized water for 5 minutes;

[0067] (2) immersing the pretreated polymer mesh in a chemical copper plating solution system, chemically depositing at 50° C. for 120 min to obtain a polymer mesh with a copper transition layer; the chemical copper plating solution includes 5 wt % copper sulfate, 2 wt % potassium sodium tartrate and 0.1 wt % glyoxylic acid;

[0068] (3) Using the prepared polymer mesh with a copper transition layer as a cathode and a phosphor copper sheet as an anode, immersing the cathode and the anode in a copper electroplating solution, wherein the copper electroplating solution includes 2 wt % copper sulfate and 5 wt % sulfuric acid; connecting a power source, and applying a current density of 5 A / dm between the anode and the cathode. 2 The current was 1.50 and the electrodeposition reaction was carried out at 30°C for 300s to obtain a polymer network-copper transition layer-porous copper plating layer composite material;

[0069] (4) Immersing the prepared polymer network-copper transition layer-porous copper plating layer composite material into a solution containing a hydrophilic polymer, wherein the solution contains 1wt% polyvinyl alcohol and the solvent is deionized water; after immersing for 30 seconds, taking it out and drying it at 30°C for 5 minutes, finally obtaining a multi-layer reinforced super hydrophilic polymer network composite material.

[0070] In the composite material obtained in this embodiment, the thicknesses of the polypropylene mesh, the copper transition layer, and the porous copper plating layer are 50μm, 10μm, and 100μm, respectively; the porosity of the porous copper plating layer is about 50%, of which the macropores with a pore size between 30 and 300μm account for about 20%, and the small pores with a pore size between 100nm and 1000nm account for about 50%; polyvinyl alcohol is attached to the pore walls of the micro-nano porous structure of the metal porous layer, but does not completely fill the pores, and the filling thickness is about 5% of the pore diameter, so that the composite material has good hydrophilicity while having good storage capacity and capillary capacity.

[0071] Figure 1 Schematic diagram of the structure of the super-hydrophilic polymer network composite material prepared in this embodiment. Figure 1 As shown, it includes a polymer mesh substrate layer, a copper transition layer formed on the polymer mesh substrate layer by chemical plating, and a porous copper layer formed on the copper transition layer by electrodeposition, wherein the porous copper layer is filled with a hydrophilic polymer. Figure 2 3 is a SEM image of the surface of the multi-layer reinforced super-hydrophilic polymer network composite material of Example 1.

[0072] Figure 3 : is a picture of the water contact angle on the surface of the multi-layer reinforced super-hydrophilic polymer network composite material. The water contact angle on the surface of the composite material prepared in this embodiment is 0°C.

[0073] Copper sheets were used as the upper and lower covers of the heat spreader, and the multi-layer reinforced super-hydrophilic polymer mesh composite material prepared above was packaged as a liquid wick. Under a test power of 5W, the temperature difference between any two points on the surface was less than 3°C.

[0074] Testing the oil-water emulsion separation performance of the multi-layer reinforced superhydrophilic polymer network composite material with a flux of 1500 L m -2 h -1 , the separation efficiency is 99.3%.

[0075] Example 2

[0076] This embodiment provides a super-hydrophilic polymer network composite material and a preparation method thereof, which specifically includes:

[0077] (1) pre-treating a 500-mesh polyethylene mesh, wherein the pre-treatment specifically comprises: immersing the polymer mesh in a 30 wt % sodium hydroxide solution at 80° C. for 5 minutes, and then ultrasonically cleaning it with deionized water for 5 minutes;

[0078] (2) immersing the pretreated polymer mesh in a chemical copper plating solution system, chemically depositing at 80° C. for 5 minutes to obtain a polymer mesh with a copper transition layer; the chemical copper plating solution includes 25 wt % cupric chloride, 60 wt % disodium ethylenediaminetetraacetic acid, and 15 wt % formaldehyde;

[0079] (3) Using the prepared polymer mesh with a copper transition layer as a cathode and a phosphor copper sheet as an anode, immersing the cathode and the anode in a copper electroplating solution, wherein the copper electroplating solution includes 20 wt % copper chloride and 20 wt % hydrochloric acid; connecting a power source, applying a current density of 200 A / dm between the anode and the cathode; 2 The current was 0.0457 W / m, and the electrodeposition reaction was carried out at 40°C for 50 seconds to generate a porous copper coating with a micro-nano structure, thereby obtaining a polymer network-copper transition layer-porous copper coating composite material;

[0080] (4) Immersing the prepared polymer mesh with a porous copper plating layer in a hydrophilic polymer solution containing 50 wt % polyethylene glycol and a solvent of deionized water; taking out after immersion for 300 s, and drying at 60° C. for 60 min, finally obtaining a multilayer reinforced super-hydrophilic polymer mesh composite material.

[0081] In the composite material obtained in this embodiment, the thicknesses of the polyethylene mesh, the copper transition layer, and the porous copper plating layer are 100 μm, 5 μm, and 200 μm, respectively.

[0082] According to tests, the water contact angle of the surface of the composite material prepared in this embodiment is 0°.

[0083] Copper sheets are used as the upper and lower covers of the heat spreader, and a multi-layer reinforced super-hydrophilic polymer mesh composite is used as the liquid wick. After packaging, the temperature difference between any two points on the surface under 5W test power is less than 3℃.

[0084] Testing the oil-water emulsion separation performance of the multi-layer reinforced superhydrophilic polymer network composite material with a flux of 1760 L m - 2 h -1 , the separation efficiency is 99.9%.

[0085] Example 3

[0086] This embodiment provides a super-hydrophilic polymer network composite material and a preparation method thereof, which specifically includes:

[0087] (1) pre-treating a 300-mesh nylon mesh, wherein the pre-treatment specifically comprises: immersing the polymer mesh in a 30 wt % sodium hydroxide solution at 80° C. for 5 minutes, and then ultrasonically cleaning it with deionized water for 5 minutes;

[0088] (2) immersing the pretreated polymer mesh in a chemical copper plating solution system, chemically depositing at 65° C. for 60 min to obtain a polymer mesh with a copper transition layer; the chemical copper plating solution includes 10 wt % copper nitrate, 30 wt % triethanolamine and 5 wt % dimethylamino borane;

[0089] (3) Using the prepared polymer mesh with a copper transition layer as a cathode and a phosphor copper sheet as an anode, immersing the cathode and the anode in a copper electroplating solution, wherein the copper electroplating solution includes 10 wt % copper sulfate and 10 wt % hydrochloric acid; connecting a power source, and applying a current density of 100 A / dm between the anode and the cathode. 2 The current was 10000 and the electrodeposition reaction was carried out at 35° C. for 150 seconds to generate a porous copper coating with a micro-nano structure, thereby obtaining a polymer network-copper transition layer-porous copper coating composite material;

[0090] (4) Immersing the prepared polymer mesh-copper transition layer-porous copper plating layer composite material into a hydrophilic polymer solution, wherein the solution contains 30 wt % of polyvinyl pyrrolidone and the solvent is deionized water; taking it out after immersion for 150 s, and drying it at 45° C. for 30 min, finally obtaining a multi-layer reinforced super hydrophilic polymer mesh composite material.

[0091] In the composite material obtained in this embodiment, the thicknesses of the nylon mesh, the copper transition layer, and the porous copper plating layer are 50 μm, 5 μm, and 200 μm, respectively.

[0092] According to tests, the water contact angle of the surface of the composite material prepared in this embodiment is 0°.

[0093] Copper sheets were used as the upper and lower covers of the heat spreader, and the multi-layer reinforced super-hydrophilic polymer mesh was used as the liquid wick. After packaging, the temperature difference between any two points on the surface was less than 3°C under a 5W test power.

[0094] Testing the oil-water emulsion separation performance of the multi-layer reinforced superhydrophilic polymer mesh material, with a flux of 1640 L m -2 h -1 , the separation efficiency is 99.8%.

[0095] Example 4

[0096] This embodiment provides a super-hydrophilic polymer network composite material and a preparation method thereof, which specifically includes:

[0097] (1) Pretreatment of a 200-mesh polypropylene mesh, the pretreatment specifically comprising: immersing the polymer mesh in a 30 wt % sodium hydroxide solution at 80° C. for 5 minutes, and then ultrasonically cleaning it with deionized water for 5 minutes.

[0098] (2) immersing the pretreated polymer mesh in a chemical copper plating solution system, chemically depositing at 70° C. for 40 min to obtain a polymer mesh with a copper transition layer; the chemical copper plating solution includes 5wt% copper sulfate, 5wt% copper chloride, 10wt% triethanolamine, 5wt% disodium ethylenediaminetetraacetate, 3wt% formaldehyde and 5wt% dimethylaminoborane;

[0099] (3) Using the prepared polymer mesh with a copper transition layer as a cathode and a phosphor copper sheet as an anode, immersing the cathode and the anode in a copper electroplating solution, wherein the copper electroplating solution includes 5wt% copper sulfate, 5wt% copper chloride, 5wt% sulfuric acid, and 5wt% hydrochloric acid; turning on a power source, and applying a current density of 100A / dm between the anode and the cathode. 2 The current was 1000 and the electrodeposition reaction was carried out at 35°C for 150 seconds to generate a porous copper coating with a micro-nano structure, thereby obtaining a polymer network-copper transition layer-porous copper coating composite material;

[0100] (4) Immersing the prepared polymer mesh-copper transition layer-porous copper plating layer composite material into a hydrophilic polymer solution containing 20 wt % polyvinyl pyrrolidone and a solvent of deionized water; taking it out after immersion for 150 s, and drying it at 45° C. for 30 min, finally obtaining a multi-layer reinforced super hydrophilic polymer mesh composite material.

[0101] In the composite material obtained in this embodiment, the thicknesses of the polypropylene mesh, the copper transition layer, and the porous copper plating layer are 200 μm, 5 μm, and 100 μm, respectively.

[0102] According to tests, the water contact angle of the surface of the composite material prepared in this embodiment is 0°.

[0103] Copper sheets were used as the upper and lower covers of the heat spreader, and a multi-layer reinforced super-hydrophilic polymer mesh composite material was used as the liquid wick package. After packaging, the temperature difference between any two points on the surface under a 5W test power was <3°C.

[0104] Testing the oil-water emulsion separation performance of the multi-layer reinforced superhydrophilic polymer network composite material with a flux of 1980 L m -2 h -1 , the separation efficiency is 99.7%.

[0105] Comparative Example 1

[0106] Comparative Example 1 is substantially the same as Example 1, except that the polymer mesh is not electrolessly plated with copper, i.e., a copper transition layer is not formed. It is found that if the copper transition layer is not first formed by electroless plating, the subsequent porous copper plating layer cannot be electroplated on the polymer mesh, thereby failing to obtain a complete multi-layer reinforced super-hydrophilic polymer mesh composite material.

[0107] Comparative Example 2

[0108] Comparative Example 2 is basically the same as Example 1, except that: the polymer mesh containing the copper transition layer is not subjected to electrodeposition, that is, a porous copper plating layer is not constructed, and the polymer mesh containing the copper transition layer is directly immersed in a solution containing a hydrophilic polymer. It is found that the hydrophilic polymer layer in the composite material prepared in this way is very easy to be lost and become ineffective.

[0109] Comparative Example 3

[0110] Comparative Example 3 is substantially the same as Example 1, except that no hydrophilic polymer layer is constructed. According to the test, the initial water contact angle of the surface of the composite material prepared in Comparative Example 3 is 0°, but after 4 days of storage, the contact angle becomes 150°.

[0111] In addition, the inventors of the present invention also conducted experiments with other raw materials and conditions listed in this specification with reference to the methods of Examples 1-4, and finally obtained a multi-layer reinforced super-hydrophilic polymer mesh material.

[0112] In summary, the present invention uses a polymer mesh as a carrier, electroplates a metal porous layer with a porous structure on the polymer mesh carrier layer through chemical-electrochemical deposition technology, and finally prepares a hydrophilic polymer layer with a super hydrophilic effect through a dip coating method; the polymer mesh filled with a hydrophilic polymer has a high porosity and good hydrophilicity, and has a high water storage capacity and capillary capacity; the functional layers complement each other's advantages and are multifunctionally coupled to form a bottom-up multi-layer reinforced super hydrophilic polymer mesh material, which can be used in the fields of heat spreader wicks, oil-water separation, etc.

[0113] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all aspects and are not intended to limit the present invention, the scope of the present invention is defined only by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

[0114] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0115] Although the present invention has been described with reference to illustrative embodiments, it will be appreciated by those skilled in the art that various other changes, omissions and / or additions may be made without departing from the spirit and scope of the present invention and that the elements of the embodiments may be replaced by substantial equivalents. In addition, many modifications may be made without departing from the scope of the present invention to adapt specific circumstances or materials to the teachings of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for performing the present invention, but it is intended that the present invention will include all embodiments within the scope of the appended claims. In addition, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. A super-hydrophilic polymer network composite material, It is characterized in that include: A polymer mesh substrate having a mesh structure formed of a polymer; A metal transition layer is coated on the polymer mesh substrate; A metal porous layer, which is coated on the metal transition layer and has a micro-nano porous structure; The hydrophilic polymer layer comprises a hydrophilic polymer filled in the metal porous layer, wherein the hydrophilic polymer comprises one or a combination of polyvinyl alcohol, polyethylene glycol or polyvinyl pyrrolidone.

2. The super-hydrophilic polymer network composite material according to claim 1, Features: The micro-nano porous structure is a capillary structure, wherein 20-50% of the pores by volume are macropores with a pore size of 30 μm to 300 μm, and 50-80% of the pores by volume are small pores with a pore size of 100 nm to 1000 nm, wherein the pore size of the macropores increases in a direction away from the polymer mesh substrate; And / or, the hydrophilic polymer is attached to the pore wall of the micro-nano porous structure, and forms a hydrophilic polymer layer on the pore wall with a thickness of 5 to 10% of the pore diameter; and / or, the porosity of the metal porous layer is 20 to 90%; And / or, the thickness ratio of the polymer mesh substrate, the metal transition layer, and the metal porous layer is 1-100: 0.05-2: 1-100; and / or, the mesh size of the polymer mesh substrate is 120 to 500 meshes; And / or, the material of the polymer mesh substrate includes one or more of polypropylene, polyethylene or nylon; the material of the metal transition layer includes copper, and the material of the metal porous layer includes copper; And / or, the contact angle between the super hydrophilic polymer network composite material and water is 0°.

3. A method for preparing a super-hydrophilic polymer network composite material, It is characterized in that include: At least one chemical plating method is used to form a metal transition layer on the surface of the polymer mesh substrate to obtain a first intermediate material; At least using an electrodeposition method to deposit a second metal on the surface of the first intermediate material to form a metal porous layer having a micro-nano porous structure, thereby obtaining a second intermediate material; The hydrophilic polymer is filled into the metal porous layer to obtain a super-hydrophilic polymer network composite material.

4. The preparation method according to claim 3, Features: The chemical plating solution used in the chemical plating comprises a soluble salt of the first metal, a complexing agent and a reducing agent; And / or, the process conditions of the chemical plating include: a plating temperature of 50 to 80° C. and a plating time of 5 to 120 min.

5. The preparation method according to claim 4, Features: The chemical plating solution comprises 5-25 wt% of a soluble salt of a first metal, 2-60 wt% of a complexing agent and 0.1-15 wt% of a reducing agent; And / or, the first metal includes copper, and the chemical plating solution includes one or a combination of copper sulfate, copper chloride or copper nitrate; And / or, the complexing agent includes one or a combination of potassium sodium tartrate, disodium ethylenediaminetetraacetate, sodium sulfosalicylate or triethanolamine; And / or, the reducing agent includes one or a combination of glyoxylic acid, formaldehyde or dimethylaminoborane.

6. The preparation method according to claim 3, Features: The electroplating solution used in the electroplating comprises a soluble salt of the second metal and an acid; And / or, the electrodeposition uses the first intermediate material as a cathode and the anode is made of phosphor copper; And / or, the process conditions of the electrodeposition include: a current density of 5 to 200 A / dm 2 , temperature is 30~40℃, time is 5~300s; And / or, the filling of the hydrophilic polymer into the metal porous layer specifically comprises: soaking the second intermediate material in a solution containing the hydrophilic polymer for 30 to 300 seconds, and drying to obtain the super hydrophilic polymer network composite material.

7. The preparation method according to claim 6, Features: The electroplating solution includes 2-20 wt % of a soluble salt of a second metal and 5-20 wt % of an acid; And / or, the second metal includes copper, and the electroplating solution includes one or a combination of copper sulfate and copper chloride; And / or, the acid includes one or a combination of sulfuric acid and hydrochloric acid.

8. The preparation method according to claim 6, Features: The hydrophilic polymer includes one or a combination of polyvinyl alcohol, polyethylene glycol or polyvinyl pyrrolidone; and / or, the solution containing the hydrophilic polymer comprises 1 to 50 wt % of the hydrophilic polymer; And / or, the drying temperature is 30-60° C., and the drying time is 5-60 min.

9. Use of the super-hydrophilic polymer network composite material according to claim 1 or 2 or the super-hydrophilic polymer network composite material prepared according to the method according to any one of claims 3 to 8 in preparing a vapor chamber wick or oil-water separation.

10. A heat spreader, comprising a shell and a liquid wick disposed inside the shell, Features: The liquid absorbent core comprises the super-hydrophilic polymer network composite material according to claim 1 or 2 or the super-hydrophilic polymer network composite material prepared by the method according to any one of claims 3-8.

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