CN115926335B - Method for constructing non-cortex porous structure on polymer surface by high-pressure gas foaming technology - Google Patents
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Abstract
The invention provides a method for constructing a non-cortex porous structure on the surface of a polymer by utilizing a high-pressure gas foaming technology, which comprises the following steps: (1) Overlapping the formed polymer blank A and the formed polymer blank B, and enabling the interfaces of the formed polymer blank A and the formed polymer blank B to be incompletely fused under the condition of heating and pressurizing to obtain a blank with incompletely fused interfaces; (2) Swelling and penetrating the blank with the incompletely fused interface by adopting high-pressure gas, and foaming the blank with the incompletely fused interface by a pressure relief method or a heating method; (3) Separating the foaming material from the interface of incomplete fusion of the foaming material to obtain a polymer A and a polymer B with porous structures on the surfaces. The top ends of the surface porous structures of the polymer A and the polymer B, the surfaces of which are provided with the porous structures, are not covered by a cortex, and the surface porous structures are arranged in a single layer. The invention can convert the polymer raw materials into products with porous surfaces, and can also increase the adjustable range of the pore structure and the surface roughness of the polymer surface.
Description
Technical Field
The invention belongs to the technical field of preparation of polymer functional materials, and relates to a method for constructing a non-cortex porous structure on the surface of a polymer by utilizing a high-pressure gas foaming technology.
Background
The porous surface has huge specific surface area and roughness, and an adjustable micro-nano structure, and the construction of the porous structure on the surface of the material has important significance for the adjustment of wettability, adhesion, packaging performance, optical performance, triboelectric performance and other performances of the material surface. For many years, people prepare a series of advanced functional polymer materials including super-hydrophobic coatings, super-smooth surfaces, tissue culture supports, catalyst carriers, radiation cooling materials and the like by constructing porous structures on the surfaces of the polymers, and the materials have great development potential in various fields such as aerospace, food packaging, biological medicines, building materials and the like. The conventional methods for constructing porous structures on the surface of polymers are numerous, and mainly include photolithography, soft lithography, physical imprinting, electrostatic spraying, microphase separation, and the like. These methods are unique and complement each other but also face challenges such as equipment, template dependence, and organic solvent use. Therefore, the development of a preparation technology of green porous surfaces which does not depend on expensive equipment, templates and organic solvents has important research significance and application value.
The high-pressure gas foaming technology is a technology for preparing a porous structure in a polymer matrix by utilizing the dependence of the solubility of high-pressure gas in the polymer on the pressure and the temperature, and enabling a polymer/gas mixed system saturated by the high-pressure gas to enter a thermodynamically unstable state in a rapid depressurization/heating mode and the like. The high-pressure gas foaming technology is independent of expensive photoetching equipment, templates and organic solvents, and is a green and clean polymer pore-forming technology. However, since the gas dissolved at the polymer surface and the vicinity thereof escapes before the gas nuclei are formed, the polymer porous material prepared by the conventional high-pressure gas foaming technique has a smooth and nonporous surface or skin layer. Therefore, how to eliminate the smooth surface/nonporous skin layer of the polymer porous material is a key problem of constructing a porous structure on the polymer surface by using the high-pressure gas foaming technology.
In order to construct a porous structure on a polymer surface by using a high-pressure gas foaming technology, researchers at home and abroad cover a limiting barrier such as a metal, a PI film, a PET film, an organosilicon compound, natural rubber and the like on the polymer surface to limit gas from escaping from the polymer surface, so as to prepare the polymer porous surface. However, these limiting barriers often cannot be converted into end products, resulting in waste of raw materials. More importantly, the difference between the polymer matrix and the limiting barrier in terms of gas solubility, gas transmission path, interfacial tension, mechanical state and the like can affect the size and geometry of the pore structure of the polymer surface, which often results in the problems of uneven pore size of the porous surface of the polymer or incomplete removal of the top cortex of the cell. For example, in polylactic acid (PLA)/Polystyrene (PS) limited systems (where PLA is the limiting barrier and PS is the limiting polymer), due to high pressure CO 2 Solubility and diffusion pathways in PLA and PS are different, resulting in CO 2 Aggregation and uneven distribution at the PLA/PS interface eventually results in uneven cell size at the PS surface. For another example, in polyimide film (PI)/polyurethane (TPU) constrained systems (where PI film is the limiting barrier and TPU is the limiting polymer), since PI film is always in the glassy state within the TPU foaming window, cells can only nucleate on the surface of the TPU phase and grow towards the inside of the TPU, eventually resulting in the TPU porous surface cell tips still leaving a partial skin layer, which greatly affects the morphology control of the TPU porous surface cell structure and limits the adjustable range of the polymer porous surface roughness; in addition, the strong interfacial forces of the PI film and the TPU, and the rigidity of the PI film itself, also greatly limit the lateral growth of cells on the porous surface of the TPU.
In summary, the existing method for constructing the porous structure on the surface of the polymer by utilizing the high-pressure gas foaming technology also has the problems of uneven pore diameter, incomplete removal of the cortex at the top end of the pore, limited pore growth, difficult control of the pore structure, narrow adjustable range of the surface roughness and the like. Therefore, if a method for constructing a porous structure on the surface of a polymer, which has the advantages of uniform surface pore diameter, no cortex residue at the top end of the pore, convenient pore structure control and wide adjustable range of surface roughness, can be developed based on a high-pressure gas foaming technology, the method has positive significance for better promoting the application of the porous surface of the polymer.
Disclosure of Invention
Aiming at the problems of uneven pore diameter, incomplete removal of the cortex at the top end of a pore, limited pore growth, difficult pore structure control and narrow adjustable range of surface roughness existing in the prior art of constructing a porous structure on the surface of a polymer based on a high-pressure gas foaming technology, the invention provides a method for constructing a non-cortex porous structure on the surface of the polymer by utilizing the high-pressure gas foaming technology, so as to improve the uniformity of the pore size of the surface of the polymer, more effectively remove the cortex at the top end of the pore on the surface of the polymer, increase the adjustable range of the pore structure and the surface roughness of the surface of the polymer, avoid limiting the waste of barriers and improve the preparation efficiency of the porous surface.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for constructing a skin-free porous structure on the surface of a polymer by utilizing a high-pressure gas foaming technology comprises the following steps:
(1) Preparing a blank with incompletely fused interfaces
Overlapping the formed polymer blank A and the formed polymer blank B at a fusion temperature T 1 Applying a fusion pressure P to the overlapped blanks 1 The interface of the molded polymer blank A and the molded polymer blank B is subjected to incomplete fusion, so that a blank with the incompletely fused interface is obtained; the molded polymer blank A and the molded polymer blank B have a common processing temperature window and a foaming temperature window, and the fusion temperature T 1 Selecting within a common processing temperature window;
(2) High pressure gas foaming
Placing the blank body with incompletely fused interfaces into a high-pressure cavity, wherein the pressure is P 2 At a temperature T 2 Swelling and penetrating the blank with incompletely fused interfaces until the high-pressure gas is saturated in the blank with incompletely fused interfacesThen foaming the blank body with the incompletely fused interfaces by a pressure relief method or a heating method, forming foam holes at the interface of the blank body with the incompletely fused interfaces, and shaping the foam holes to obtain a foaming material; temperature T 2 Selecting in a foaming temperature window common to the molded polymer blank A and the molded polymer blank B;
(3) Separating porous surfaces of polymers
Separating the foaming material from the incompletely fused interface of the foaming material obtained in the step (2), and simultaneously obtaining a polymer A with a porous structure on the surface and a polymer B with a porous structure on the surface;
the top of the surface porous structure of the polymer A with the surface porous structure and the polymer B with the surface porous structure is not covered by a cortex, and the surface porous structure is arranged in a single layer; the polymer A with the porous structure on the surface and the polymer B with the porous structure on the surface are respectively formed by converting a molded polymer blank A and a molded polymer blank B at two sides of an incompletely fused interface.
In the technical scheme, the formed polymer blank A is prepared from an amorphous polymer, a crystalline polymer or rubber with the crosslinking degree of 30-60%, and the formed polymer blank B is prepared from an amorphous polymer, a crystalline polymer or rubber with the crosslinking degree of 30-60%.
Further, assuming that the molded polymer body A and the molded polymer body B are prepared from the polymer A and the polymer B, respectively, the polymer selected and the fusion temperature T 1 And temperature T 2 The following requirements should be met:
fusion temperature T when shaped polymer body A and shaped polymer body B are made from the same amorphous polymer 1 Should satisfy T g -10℃≤T 1 ≤T g +30 ℃, temperature T 2 Should satisfy T g -70℃≤T 2 ≤T g +30℃，T g Is the glass transition temperature of the polymer;
when the shaped polymer body A and the shaped polymer body B are prepared from different amorphous polymers A and B, the glass of the polymers A and BThe glass transition temperature is less than or equal to-30 ℃ and less than or equal to T g Polymer A -T g Polymer B Let T be less than or equal to 30 DEG C g Polymer A ＞T g Polymer B Fusion temperature T 1 Should satisfy T g Polymer A -10℃≤T 1 ≤T g Polymer B +30 ℃, temperature T 2 Should satisfy T g Polymer A -70℃≤T 2 ≤T g Polymer B +30℃，T g Polymer A Is the glass transition temperature, T, of polymer A g Polymer B Is the glass transition temperature of polymer B;
fusion temperature T when shaped polymer body A and shaped polymer body B are made from the same crystalline polymer 1 Should satisfy T m -100℃≤T 1 ≤T m Temperature T 2 Should satisfy T m -100℃≤T 2 ≤T m ，T m Is the melting point of the polymer;
when the molding polymer blank A and the molding polymer blank B are prepared from different crystalline polymers A and B, the melting points of the polymers A and B should satisfy the temperature T of minus 30 DEG C m Polymer A -T m Polymer B The temperature is less than or equal to 30 ℃; let T be m Polymer A ＞T m Polymer B Fusion temperature T 1 Should satisfy T m Polymer A -100℃≤T 1 ≤T m Polymer A Temperature T 2 Should satisfy T m Polymer A -100℃≤T 2 ≤T m Polymer A ，T m Polymer A T is the melting point of Polymer A m Polymer B Is the melting point of polymer B;
when the molding polymer body A and the molding polymer body B are respectively prepared from an amorphous polymer A and a crystalline polymer B, the glass transition temperature of the polymer A and the melting point of the polymer B should satisfy a temperature of-30 ℃ to T g Polymer A -T m Polymer B Let T be less than or equal to 30 DEG C g Polymer A ＞T m Polymer B Fusion temperature T 1 Should satisfy T g Polymer A -10℃≤T 1 ≤T g Polymer A +30 ℃, temperature T 2 Should satisfy T g Polymer A -70℃≤T 2 ≤T g Polymer A +30℃; let T be g Polymer A ＜T m Polymer B Fusion temperature T 1 Should satisfy T m Polymer B -100℃≤T 1 ≤T m Polymer B +30 ℃, temperature T 2 Should satisfy T m Polymer B -100℃≤T 2 ≤T m Polymer B +30℃；
When the molding polymer blank A and the molding polymer blank B are prepared from the same rubber, the crosslinking degree of the molding polymer blank A and the molding polymer blank B is between 30 and 60 percent, and the fusion temperature T is 1 The temperature is less than or equal to 0 ℃ and less than or equal to T 1 ≤T v Temperature T 2 The temperature is less than or equal to 0 ℃ and less than or equal to T 2 ≤T v ，T v Is the vulcanization temperature of rubber;
when the molding polymer blank A and the molding polymer blank B are prepared from different rubbers A and B, the crosslinking degree of the molding polymer blank A and the molding polymer blank B is between 30% and 60%, and the vulcanization temperature of the rubbers A and B is less than or equal to minus 30 ℃ and less than or equal to T vA -T vB The temperature is less than or equal to 30 ℃; let T be vA ＞T vB Fusion temperature T 1 The temperature is less than or equal to 0 ℃ and less than or equal to T 1 ≤T vB Temperature T 2 The temperature is less than or equal to 0 ℃ and less than or equal to T 2 ≤T vB ，T vA T is the vulcanization temperature of rubber A vB Is the vulcanization temperature of rubber B;
when the molded polymer body A is prepared from the polymer A and the polymer A is rubber, and the molded polymer body B is prepared from the amorphous or crystalline polymer B, the crosslinking degree of the molded polymer body A is between 30 and 60 percent, and the glass transition temperature T of the polymer B is between g Or melting point T m The temperature is less than or equal to 0 ℃ and less than or equal to (T) g Or T m )≤T v Fusion temperature T 1 Should satisfy (T) g Or T m )≤T 1 ≤T v Temperature T 2 Should satisfy (T) g Or T m )≤T 2 ≤T v ，T v Is the vulcanization temperature of polymer a.
In the above technical solution, when the molded polymer body a and/or the molded polymer body B is rubber, after foaming in the step (2), a post-vulcanization operation is required to fix the cell structure.
In the step (1) of the above technical scheme, the number of the adopted molded polymer blanks A is at least one, the number of the adopted molded polymer blanks B is at least one, when the number of the molded polymer blanks A or the molded polymer blanks B exceeds one, the molded polymer blanks A and the molded polymer blanks B are alternately overlapped, and at the fusion temperature T 1 Applying a fusion pressure P to the overlapped blanks 1 And (3) enabling the interface of the molded polymer blank A and the molded polymer blank B to be incompletely fused, so as to obtain a blank with incompletely fused interface. When the number of the molded polymer bodies a or B used exceeds one, a polymer having a porous structure on one surface and both surfaces can be prepared at the same time.
In the technical scheme, the shapes of the surfaces which are contacted with each other after the formed polymer blank A and the formed polymer blank B are overlapped are matched with each other. For example, the surfaces of the molded polymer body A and the molded polymer body B which are in contact with each other may be flat surfaces, or concave surfaces and convex surfaces which are matched with each other, at the fusion pressure P 1 Under the condition, the surfaces of the molded polymer blank A and the molded polymer blank B which are in contact with each other can be attached together. For ease of processing, the surfaces of the shaped polymer body a and the shaped polymer body B that contact each other are preferably planar.
In the above technical solution, the fusion pressure P in the step (1) 1 The pressure is usually 1 to 30MPa, preferably 3 to 20MPa, depending on the nature of the molded polymer body. Further, at the fusion temperature T 1 Applying a fusion pressure P to the overlapped blanks 1 The duration of the process of (2) is preferably 1 to 60 minutes.
In the above technical solution, the "incomplete interfacial fusion" in the blank with incomplete interfacial fusion means that the chain ends of the surface molecular chains of the molded polymer blank A and the molded polymer blank B in close contact are at the fusion temperature T 1 And fusion pressure P 1 And the mechanical properties of the fused interface are lower than the intrinsic mechanical properties of the polymer A and the polymer B. By adjusting the fusion temperature T 1 Fusion pressure P 1 At a fusion temperature T 1 And fusion pressure P 1 The fusion degree of the polymer interface can be regulated and controlled by the contact time. The degree of interfacial fusion can be obtained by measuring the adhesive strength of the interface.
In the above technical solution, the molded polymer body a and/or the molded polymer body B may further include a filler. Further, when the filler is contained in the molded polymer body a or the molded polymer body B, the content of the filler is generally not more than 50% by mass of the polymer in the molded polymer body a or the molded polymer body B. In practical application, the type of the filler can be selected and the addition amount of the filler can be determined according to specific application requirements. The filler includes at least one of a filler that imparts magnetic, fluorescent, targeted, electrically conductive, thermally conductive, catalytic properties to the material, and a reinforcing filler. For example, common fillers include: silica, montmorillonite, glass beads, graphene, carbon nanotubes, graphite, gold, palladium, titanium oxide, aluminum oxide, ferroferric oxide, zinc oxide, boron nitride, peroxide, a catalyst-based filler, a fluorescent-based filler, and a hydrophobic/hydrophilic dye. The filler may be spherical, platelet, tubular or irregular nanoparticles, and is typically between 1nm and 1 μm in size. The form, size and dosage of the filler have certain influence on the pore structure and pore density of the prepared material, and can be adjusted according to actual requirements during application.
In the technical scheme, the pore diameter and the surface roughness of the surface porous structure of the polymer A with the porous structure on the surface and the polymer B with the porous structure on the surface can be regulated and controlled by regulating and controlling the types of the polymers in the blank body with the incompletely fused interfaces, the fusion degree of the interfaces of the blank body with the incompletely fused interfaces and the foaming conditions. Further, the regulation and control range of the pore diameters of the surface porous structures of the polymer A with the porous structure and the polymer B with the porous structure is between 100nm and 100 mu m, and the regulation and control range of the surface roughness of the polymer A with the porous structure and the polymer B with the porous structure is between 100nm and 20 mu m.
In the technical scheme, the pore size distribution form and pore morphology of the surface porous structure of the polymer A with the porous structure on the surface and the polymer B with the porous structure on the surface can be regulated and controlled by regulating and controlling the types of the polymers in the blank body with the incompletely fused interfaces, the fusion degree of the interfaces of the blank body with the incompletely fused interfaces and the foaming conditions. For example, the pore size distribution may be unimodal (unimodal pore structure) or bimodal (bimodal pore structure); the pore morphology may be either individual cells (continuous cell walls) or connected cells (discontinuous cell walls).
In the above technical solution, the foaming in the step (2) by a pressure relief method or a temperature rising method means foaming by changing the pressure or/and the temperature in the high-pressure cavity one or more times. For example, the foaming can be performed by adopting a single pressure relief mode, a single temperature rise mode, a plurality of pressure relief modes, a plurality of temperature rise modes, a first temperature rise and then pressure relief mode, a plurality of temperature rise and pressure relief alternating mode, and the like, and the cell structure of the surface of the obtained material can be adjusted by changing the specific process conditions and operation of a pressure relief method or a temperature rise method.
In the step (2) of the above technical scheme, the high-pressure gas used as the foaming agent may be one or more of carbon dioxide, nitrogen, argon, helium, air and lower alkane, wherein the lower alkane generally refers to alkane with carbon number not more than 8, and butane, pentane and the like are commonly used.
In the step (2) of the above technical scheme, the pressure P of the high-pressure gas 2 The foaming process and the nature of the blank with incompletely fused interface are selected, and are usually 1 to 30MPa, preferably 5 to 28MPa.
The surface porous structure of the polymer A with the porous structure on the surface and the polymer B with the porous structure on the surface, prepared by the invention, has the following characteristics:
The top ends of the porous structures of the surfaces of the polymers (namely, the polymer A with the porous structure on the surface and the polymer B with the porous structure on the surface) are completely uncovered by the skin layers, and the porous structures on the surfaces of the polymers are arranged in a single layer. And, when the size of the porous structure of the polymer surface is substantially uniform, the depth of the porous structure and the arrangement depth are also substantially uniform; for example, when the polymer surface has a uniform unimodal porous structure, the depth of all pore structures as well as the alignment depth are substantially uniform; for another example, when the polymer surface has a bimodal pore multi-structure, the depth and arrangement depth of the macropores in the bimodal porous structure are substantially uniform, and the depth and arrangement depth of the micropores in the bimodal porous structure are also substantially uniform. The pore size, pore morphology and pore size distribution of the porous structure of the polymer surface can be adjusted by controlling the processing technique.
The method of the present invention can form a porous structure surface having the above characteristics, mainly for the following reasons:
as shown in figure 9, a, in the prior art barrier-confining process foaming process, the barrier-confining material is typically in a glassy state, while the polymer-confining material is typically in a highly elastic or viscous state, so that cells can only nucleate at the surface of the polymer-confining material and grow toward the interior of the polymer-confining material. In this case, the geometry of the pores on the resulting polymer surface is related to the interfacial tension between the confining barrier/confining polymer/high pressure gas. In known constrained foaming systems, the geometry of the cells on the polymer surface mostly takes on a "bowl" shape due to the effect of interfacial tension, so that part of the skin remains at the top of the cells on the polymer surface. In the a-graph of fig. 9, θ 1 Gamma, the wetting angle of the polymer on the limiting barrier lg Gamma, the interfacial tension between the polymer and the foaming gas sg Gamma, which is the interfacial tension between the barrier and the foaming gas sl Is the interfacial tension between the polymer and the confining barrier.
As shown in fig. 9B, in the method of the present invention, the molded polymer body a and the molded polymer body B are both in a high-elastic state or a viscous state during foaming, and cells nucleate in the middle of the interface between the molded polymer body a and the molded polymer body B and grow toward the inside of the polymer a and the polymer B on both sides of the interface, so that there is no skin residue at the top of the porous structure of the prepared polymer surface. In diagram b of FIG. 9, θ A Is the angle between the cells and the interface of the surface of the polymer A，θ B Gamma is the angle between the cells and the interface of the surface of the polymer B Ag Gamma, the interfacial tension between polymer a and the foaming gas Bg Is the interfacial tension between polymer B and the foaming gas.
In addition, the method of the invention can convert all polymer raw materials into products with porous surfaces, and can doubly or multiply improve the preparation efficiency of the porous surfaces.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial technical effects:
1. The invention provides a method for constructing a non-skin porous structure on the surface of a polymer by utilizing a high-pressure gas foaming technology, which is characterized in that a blank body with incompletely fused interfaces is constructed by a formed polymer blank body A and a formed polymer blank body B which have a common processable temperature range, then the high-pressure gas foaming technology is utilized for foaming, and then products formed by foaming the formed polymer blank body A and the formed polymer blank body B are separated from the incompletely fused interfaces, so that the polymer with porous structures on two surfaces is obtained at the same time, the top ends of the surface porous structures of the polymer with the porous structures on the two surfaces are not covered by skins, and the surface porous structures are arranged in a single layer. By adopting the method, all raw materials can be converted into the polymer with the surface porous structure, and compared with the existing limiting barrier foaming technology, the method can double or multiple times improve the production efficiency, and has the characteristics of no waste of raw materials and higher production efficiency.
2. In the method of the invention, the molded polymer blanks on both sides of the interface are gas-limiting barriers and at the foaming temperature T 2 Under the condition of high-elastic state or viscous state, the foam cells can nucleate in the middle of the interface and grow towards the inside of the polymer at two sides of the interface, so that the problems of uneven surface pore size, incomplete removal of the top cortex of the porous structure, limited pore growth, narrow regulation range of the pore structure and roughness and the like caused by different foaming properties of a limiting barrier and a polymer matrix can be fundamentally eliminated. Is beneficial to regulating the polymer in a wider range The pore structure and surface roughness of the porous surface further optimize the surface properties.
3. The non-cortical porous structure of the polymer surface prepared by the method has the advantages that the holes are distributed on the polymer surface in a single layer, the top end of the polymer surface porous structure is covered by the non-cortical layer, and the pore diameter and the surface roughness of the porous structure and the pore diameter distribution form and the pore morphology of the polymer surface porous structure can be flexibly regulated and controlled in a wider range by regulating the types of the polymers in the blank body with incompletely fused interfaces, the fusion degree of the polymer interfaces of the blank body with incompletely fused interfaces and the foaming condition. For example, the roughness of the polymer surface can be flexibly regulated and controlled between 100nm and 20 mu m by adopting the method of the invention, and the roughness value of the porous surface of the polymer prepared by the high-pressure gas foaming technology of the gas diffusion limiting barrier in the prior art can only reach 480nm at maximum. For another example, the porous structure of the polymer surface prepared by the method of the invention can be unimodal or bimodal, and the pore morphology can have continuous or discontinuous cell walls. The method effectively widens the regulation and control range of the aperture and the surface roughness of the polymer surface, has the characteristic of good adjustability and controllability, and can better meet the application requirements of different scenes.
Drawings
Fig. 1 (a) is a surface morphology of the PS foam material having a porous structure on the surface prepared in example 1, and fig. 1 (b) is a cross-sectional morphology of the foam material prepared in step (2) of example 1, wherein the area outlined by the box is at the PS-PS interface.
Fig. 2 is a surface morphology of the PS foam material having a porous structure on the surface prepared in comparative example 1.
Fig. 3 is a surface morphology of the PS foam material having a porous structure on the surface prepared in example 2.
Fig. 4 is a surface morphology of the TPU foam material having a porous structure on the surface prepared in example 3.
Fig. 5 is a surface morphology of the porous TPU foam prepared in comparative example 2.
FIG. 6 is a surface morphology of the PS/CNT composite foam material having a porous structure on the surface prepared in example 4.
Fig. 7 (a) and (b) are respectively the surface morphology of the PS foam having a porous structure on the surface and the PMMA foam having a porous structure on the surface prepared in example 5.
Fig. 8 is a PS foam material with a porous structure on the surface prepared in example 6, wherein the area outlined by the box is the surface morphology.
Fig. 9 is a schematic diagram of the mechanism of the conventional limiting barrier method and the method of the present invention.
Detailed Description
The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technique according to the present invention will be described further by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since numerous insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure, and yet remain within the scope of the invention.
Example 1
In this example, polystyrene (PS) and CO were used as raw materials 2 The method is characterized by constructing a skin-free porous structure on the surface of PS (polystyrene) as a foaming agent, and comprises the following steps:
(1) And (3) pressing the PS granules into PS plates with the thickness of 0.5mm, overlapping the two PS plates together to enable the surfaces of the two PS plates to be attached, and pressing for 10min at the temperature of 100 ℃ and the pressure of 10MPa to enable the interfaces of the two PS plates to be incompletely fused, so as to obtain a blank body with incompletely fused PS-PS interfaces.
(2) Placing the blank body with incompletely fused interface prepared in the step (1) into an autoclave, and introducing CO into the autoclave 2 Swelling permeation is carried out by controlling the pressure in the autoclave to be 20MPa and the temperature to be 80 ℃ for 2h, CO 2 Saturated in the blank with incompletely fused interface, then pressure relief foaming is carried out at an average pressure relief rate of 10MPa/s, cells are formed at the interface of the blank with incompletely fused interface, and in fact, the process also forms a cell structure in two PS plates, so that foaming is obtained A bubble material.
(3) Separating the foaming material from the interface of incomplete fusion of the foaming material obtained in the step (2) to obtain two PS foaming materials with porous structures on the surfaces.
Fig. 1 (a) shows the surface morphology of the foamed material having a porous structure on the surface prepared in example 1, and it is understood that pores of uniform size are arranged in a single layer on the surface of the PS foamed material, the top of the porous structure on the surface of the PS foamed material is completely free from the skin layer, and the depths of all the pore structures and the arrangement depths are substantially uniform. FIG. 1 (b) is a cross-sectional profile of the foamed material prepared in step (2) of example 1, wherein the area outlined by the box is at the PS/PS interface, and it can be seen from this figure that a porous structure is generated on both sides of the PS/PS interface. Compared with the method for constructing the porous structure on the surface of the polymer by adopting a sacrificial limiting barrier mode in the prior art, the method provided by the invention has the advantages that raw materials are not wasted, and the efficiency of constructing the porous structure on the surface of the polymer is obviously improved.
Roughness test shows that the surface of the PS foaming material prepared in the embodiment has a porous structure, and the roughness value R of the porous surface of the PS foaming material q Up to 3.2 μm.
Comparative example 1
In this comparative example, a conventional limiting barrier method was used, wherein PS was used as the raw material, PI film was used as the limiting barrier, and CO was used 2 For foaming the gas, a porous structure was built on the PS surface to be compared with example 1, illustrating the difference in porous surface built by the two methods.
(1) And (3) covering the PS granules with a PI film, pressing the PS granules for 10min at 10MPa on compression molding equipment at 200 ℃, and cooling the PS granules to normal temperature to obtain a green body with a Polymer (PS) -limiting barrier (PI) interface, wherein the green body is a plate with the thickness of 0.5mm, and one surface of the green body is covered with the PI film.
(2) Placing the green body prepared in the step (1) into an autoclave, and introducing CO into the autoclave 2 Swelling and permeation are carried out under the conditions that the pressure in the autoclave is controlled to be 20MPa and the temperature is controlled to be 80 ℃, the swelling and permeation time is 2h, then the pressure relief foaming is carried out at the average pressure relief rate of 10MPa/s, and the polymer is obtainedThe porous structure is formed at the limiting barrier interface and inside the polymer, resulting in a foamed material.
(3) And (3) peeling the PI film from the surface of the foaming material obtained in the step (2) to obtain the PS foaming material with the porous structure on the surface.
Fig. 2 is a surface morphology of the PS foam material having a porous structure on the surface prepared in comparative example 1, and it can be seen from the figure that the top ends of the pore structure on the surface of the PS foam material are covered with the remaining skin layer, resulting in incomplete opening of the pore structure on the surface, and thus the roughness of the surface of the PS foam material having a porous structure prepared in this comparative example is relatively low. The roughness test showed that the comparative example has a roughness value R of the porous surface of a PS foamed material having a porous structure on the surface prepared under the same foaming conditions as in example 1 q Is 1.1 μm, which is significantly lower than the roughness of the porous surface of the PS foam material having a porous structure on the surface prepared in example 1.
Example 2
In this example, polystyrene (PS) and CO were used as raw materials 2 For foaming agent, constructing a porous structure with no cortex and discontinuous pore walls on the surface of PS, and the steps are as follows:
(1) And (3) pressing the PS granules into PS plates with the thickness of 0.5mm, overlapping the two PS plates together to enable the surfaces of the two PS plates to be attached, and pressing for 10min under the conditions of 120 ℃ and 10MPa to enable the interfaces of the two PS plates to be incompletely fused, so as to obtain a blank body with incompletely fused PS-PS interfaces.
(2) Placing the blank body with incompletely fused interface prepared in the step (1) into an autoclave, and introducing CO into the autoclave 2 Controlling the pressure in the autoclave to be 28MPa and the temperature to be 40 ℃ for swelling and permeation, swelling permeation time is 4h, CO 2 Saturated in the blank body with incompletely fused interfaces is achieved, then pressure relief foaming is carried out at an average pressure relief rate of 20MPa/s, cells are formed at the interfaces of the blank body with incompletely fused interfaces, and in fact, a cell structure is formed in the two PS plates in the process, so that the PS foaming material is obtained.
(3) Separating the foaming material from the interface of incomplete fusion of the foaming material obtained in the step (2) to obtain two PS foaming materials with porous structures on the surfaces.
Fig. 3 is a surface morphology of the PS foam material having a porous structure on the surface prepared in example 2, and it is understood from this figure that the surface morphology of the PS foam material having a porous structure on the surface prepared in this example is significantly different from that in example 1, pores of the porous surface are interconnected, cell walls are discontinuous, the porous surface takes a "needle-mat" shape, and the top of the porous surface is completely free of a skin layer. Roughness test shows that the surface of the PS foaming material prepared in the embodiment has a porous structure, and the roughness value R of the porous surface of the PS foaming material q 619nm.
It is known from examples 1 to 2 that the pore morphology of the porous surface can be controlled by controlling the foaming conditions in step (2) and the degree of fusion of the polymer interfaces of the green body in which the interfaces constructed in step (1) are not completely fused.
Example 3
In this example, crystalline polyurethane (TPU) is used as the starting material, N 2 For the foaming agent, a skin-free porous structure is constructed on the surface of the TPU, and the steps are as follows:
(1) Pressing TPU granules into TPU plates with the thickness of 0.3mm, overlapping two TPU plates together to enable the surfaces of the two TPU plates to be attached, and pressing for 5min under the conditions of 170 ℃ and 10MPa to enable the interfaces of the two TPU plates to be incompletely fused, so as to obtain a blank body with the incompletely fused TPU-TPU interfaces.
(2) Placing the blank body with incompletely fused interface prepared in the step (1) into an autoclave, and introducing N into the autoclave 2 Swelling permeation is carried out by controlling the pressure in the autoclave to be 5MPa and the temperature to be 10 ℃, the swelling permeation time is 20h, and N is the same as that of the autoclave 2 And (3) saturation is achieved in the blank body with the incompletely fused interface, then pressure relief is carried out at an average pressure relief rate of 2MPa/s, the blank body with the incompletely fused interface after the saturation is taken out is placed in an oil bath with the temperature of 120 ℃ for foaming for 1min, foam cells are formed at the interface of the blank body with the incompletely fused interface, and in fact, a foam cell structure is formed in two TPU plates in the process, so that the TPU foaming material is obtained.
(3) Separating the foaming material from the interface of incomplete fusion of the foaming material obtained in the step (2) to obtain two TPU foaming materials with porous structures on the surfaces.
Fig. 4 is a surface morphology of the TPU foam material having a porous structure on the surface prepared in example 3, and it is understood from the figure that pores having a uniform size are arranged in a single layer on the surface of the TPU foam material, and the top of the porous structure of the surface is completely free from the skin layer. Roughness test shows that the surface of the TPU foaming material with the porous structure prepared in the embodiment has a roughness value R q Up to 5.4 μm.
Comparative example 2
In this comparative example, the fusion temperature T was adjusted based on example 3 1 . For comparison with example 3, the importance of controlling the fusion temperature in step (1) is demonstrated.
(1) Pressing TPU granules into TPU plates with the thickness of 0.3mm, overlapping two TPU plates together to enable the surfaces of the TPU plates to be attached, and pressing for 5min at 140 ℃ and 10MPa to obtain a blank body.
(2) Placing the green body prepared in the step (1) into an autoclave, and introducing N into the autoclave 2 Swelling permeation is carried out by controlling the pressure in the autoclave to be 5MPa and the temperature to be 10 ℃, the swelling permeation time is 20h, and N is the same as that of the autoclave 2 And (3) saturated in the blank, then releasing pressure at an average pressure release rate of 2MPa/s, taking out the saturated blank, and placing the blank in an oil bath with the temperature of 120 ℃ for foaming for 1min to obtain the TPU foaming material.
(3) And (3) applying external force to two sides of the foaming material obtained in the step (2) to separate the two foaming materials, so as to obtain two TPU foaming materials.
Fig. 5 is a surface morphology of the TPU foam prepared in comparative example 2, and it can be seen from this figure that the surface of the TPU foam prepared in this comparative example has no pore structure.
Example 4
In this embodiment, a composite material of PS and multiwall Carbon Nanotubes (CNT) (PS/CNT composite material) is used as a raw material, a mixed gas of nitrogen and butane is used as a foaming agent, and a skin-free porous structure is constructed on the surface of the PS/CNT composite material, which comprises the following steps:
(1) 95 parts by mass of the PS pellets and 5 parts by mass of CNTs were charged into an internal mixer, and melt-blended at 200℃for 10 minutes at a rotation speed of 50rpm, to obtain a PS/CNT composite. The PS/CNT composite material is pressed into a PS/CNT composite material plate with the thickness of 0.5mm, two PS/CNT composite material plates are taken to be overlapped together to enable the surfaces of the two PS/CNT composite material plates to be attached, and the PS/CNT composite material plate is pressed for 20min under the conditions of 130 ℃ and 5MPa, so that the interfaces of the two PS/CNT composite material plates are incompletely fused, and a blank body with incompletely fused PS/CNT-PS/CNT interfaces is obtained.
(2) Placing the blank body with the incompletely fused interface prepared in the step (1) in an autoclave, introducing mixed gas of nitrogen and butane into the autoclave, controlling the pressure in the autoclave to be 12MPa, and the temperature to be 70 ℃ for swelling and permeation, wherein the swelling and permeation time is 4h, the mixed gas of the nitrogen and the butane is saturated in the blank body with the incompletely fused interface, then releasing pressure and foaming at the average pressure release rate of 12MPa/s, forming foam cells at the interface of the blank body with the incompletely fused interface, and forming a foam cell structure in the two PS/CNT composite material plates in the process to obtain the foaming material.
(3) Separating the foaming material from the incompletely fused interface of the foaming material obtained in the step (2) to obtain the PS/CNT composite foaming material with the porous structure on the two surfaces.
Fig. 6 is a surface morphology of the PS/CNT composite foam having a porous structure on the surface prepared in example 4, and it is understood from the figure that pores having a uniform size are arranged in a single layer on the surface of the PS/CNT composite foam, and the top of the surface porous structure is completely free from the skin layer.
Example 5
In this example, polymethyl methacrylate (PMMA) and PS are used as the raw materials, and N 2 The foaming agent is used for constructing a skin-free porous structure on the surfaces of PMMA and PS at the same time, and the steps are as follows:
(1) Respectively pressing PMMA granules and PS granules into plates with the thickness of 0.5mm, overlapping a PMMA plate and a PS plate together to enable the surfaces of the PMMA plate and the PS plate to be attached, and pressing for 20min at 150 ℃ and 10MPa to enable the interfaces of the PMMA plate and the PS plate to be incompletely fused, thus obtaining a blank body with incompletely fused PMMA-PS interfaces.
(2) The interface prepared in the step (1) is incompletely fusedPlacing the green body in an autoclave, and introducing N into the autoclave 2 Controlling the pressure in the autoclave to be 16MPa and the temperature to be 60 ℃ for swelling permeation, wherein the swelling permeation time is 2h, N 2 Saturated in the blank with incompletely fused interfaces is achieved, then pressure relief foaming is carried out at an average pressure relief rate of 10MPa/s, cells are formed at the interfaces of the blank with incompletely fused interfaces, and in fact, a cell structure is formed in PMMA and PS plates in the process, so that the foaming material is obtained.
(3) Separating the foaming material from the interface of incomplete fusion of the foaming material obtained in the step (2) to obtain the PMMA foaming material with the porous structure on the surface and the PS foaming material with the porous structure on the surface.
The two graphs (a) and (b) of fig. 7 are the surface morphology of the PS foam material having a porous structure on the surface and the PMMA foam material having a porous structure on the surface prepared in example 5, respectively, and it is clear from the graph that the pores are arranged in a single layer on the surfaces of the PS foam material and the PMMA foam material, the pore sizes of the surfaces are different, and the top ends of the porous structures of the surfaces are completely free from the skin layer.
Example 6
In this embodiment, PS is used as the raw material, and N is used as the raw material 2 The method is characterized in that a skin-free porous structure is constructed on the PS surface for a foaming agent, and the PS surface has a bimodal cell structure by adjusting foaming process parameters, and comprises the following steps:
(1) And (3) pressing the PS granules into PS plates with the thickness of 0.2mm, overlapping the two PS plates together to enable the surfaces of the two PS plates to be attached, and pressing for 5min under the conditions of 120 ℃ and 5MPa to enable the interfaces of the two PS plates to be incompletely fused, so as to obtain a blank body with incompletely fused PS-PS interfaces.
(2) Placing the blank body with incompletely fused interface prepared in the step (1) into an autoclave, and introducing N into the autoclave 2 Swelling permeation is carried out by controlling the pressure in the autoclave to be 18MPa and the temperature to be 40 ℃, the swelling permeation time is 5h, and N is the same as that of the autoclave 2 Saturated in the blank with incomplete fusion at the interface, then the temperature of the autoclave is raised to 100 ℃ at the heating rate of 10 ℃/min, the autoclave is kept for 30min, and then the blank with incomplete fusion at the interface is subjected to pressure relief foaming at the average pressure relief rate of 10MPa/sThe cells are formed at the interface of the two PS plates, and in fact the process also forms a cell structure in the two PS plates, resulting in a foamed material.
(3) Separating the foaming material from the interface of incomplete fusion of the foaming material obtained in the step (2) to obtain two PS foaming materials with porous structures on the surfaces.
Fig. 8 is a surface morphology of the PS foam material having a porous structure on the surface prepared in example 6, and it is understood from this figure that pores having a bimodal cell structure, i.e., both macropores and micropores, are arranged in a single layer on the surface of the PS foam material, and the top of the surface porous structure is completely free of skin coverage. Compared with example 1, it is demonstrated that the method of the present invention can flexibly adjust the pore structure of the surface by adjusting the foaming condition of step (2).
Example 7
In this embodiment, PS is used as the raw material, and N is used as the raw material 2 As a foaming agent, a skin-free porous structure was constructed on one and both surfaces of PS, as follows:
(1) And pressing the PS granules into PS plates with the thickness of 0.3mm, overlapping three PS plates together, respectively attaching two surfaces of the PS plates positioned in the middle layer to one surface of the PS plates positioned in the upper layer and the lower layer, and pressing for 10min under the conditions of 115 ℃ and 15MPa, so that two interfaces (an interface between the upper layer and the PS plates in the middle layer and an interface between the middle layer and the PS plates in the lower layer) of the three PS plates are incompletely fused, and a blank body with incompletely fused PS-PS-PS interfaces is obtained.
(2) Placing the blank body with incompletely fused interface prepared in the step (1) into an autoclave, and introducing N into the autoclave 2 Controlling the pressure in the autoclave to be 20MPa and the temperature to be 80 ℃ for swelling permeation, wherein the swelling permeation time is 3h, N 2 Saturated in the blank with incompletely fused interfaces is achieved, then pressure relief foaming is carried out at an average pressure relief rate of 10MPa/s, cells are formed at the interfaces of the blank with incompletely fused interfaces, and in fact, a cell structure is formed in three PS plates in the process, so that the foaming material is obtained.
(3) Separating the foaming material from the incompletely fused interface of the foaming material obtained in the step (2) to obtain two PS foaming materials with porous structures on one surface and one PS foaming material with porous structures on the upper surface and the lower surface.
Example 8
In this embodiment, raw silicone rubber is used as the raw material, and N is used as the raw material 2 The foaming agent is a foaming agent, and a skin-free porous structure is constructed on the surface of the silicon rubber, and the steps are as follows:
(1) 100 parts by mass of a raw silicone rubber, 20 parts by mass of white carbon black, 5 parts by mass of a hydroxyl silicone oil and 1.5 parts by mass of a vulcanizing agent (dicumyl peroxide, DCP) were added into an internal mixer and kneaded for 20 minutes to obtain a rubber compound. The mixed rubber is placed on a flat vulcanizing machine to be pressed into a silicon rubber blank with the thickness of 0.3mm, and the silicon rubber blank is kept for 15min under the conditions of 140 ℃ and 10MPa, so that the crosslinking degree of the silicon rubber blank reaches about 60 percent. And (3) superposing the two obtained silicon rubber blanks with a certain crosslinking degree, and pressing for 2min at 25 ℃ and 1MPa to ensure that the interfaces of the two silicon rubber blanks are incompletely fused, thus obtaining the blank with incompletely fused silicon rubber-silicon rubber interfaces.
(2) Placing the blank body with incompletely fused interface prepared in the step (1) into an autoclave, and introducing N into the autoclave 2 Swelling permeation is carried out by controlling the pressure in the autoclave to be 12MPa and the temperature to be 40 ℃, the swelling permeation time is 0.5h, and N is the same as that of the autoclave 2 Saturated in the blank with incompletely fused interface, then releasing pressure and foaming at an average pressure releasing rate of 2MPa/s, generating cells at the interface of the blank with incompletely fused interface, and then placing the cells in an oven at 200 ℃ for continuous vulcanization for 1h to obtain the foaming material.
(3) Separating the foaming material from the interface of incomplete fusion of the foaming material obtained in the step (2) to obtain two pieces of silicon rubber foaming material with porous structures on the surfaces.
Claims (10)
1. A method for constructing a skin-free porous structure on the surface of a polymer by utilizing a high-pressure gas foaming technology is characterized by comprising the following steps:
(1) Preparing a blank with incompletely fused interfaces
Shaping the polymer blank A and shaping and polymerizingOverlapping the blank bodies B at the fusion temperature T 1 Applying a fusion pressure P to the overlapped blanks 1 The interface of the molded polymer blank A and the molded polymer blank B is subjected to incomplete fusion, so that a blank with the incompletely fused interface is obtained; the molded polymer blank A and the molded polymer blank B have a common processing temperature window and a foaming temperature window, and the fusion temperature T 1 Selecting within a common processing temperature window;
(2) High pressure gas foaming
Placing the blank body with incompletely fused interfaces into a high-pressure cavity, wherein the pressure is P 2 At a temperature T 2 Swelling and penetrating the blank with the incompletely fused interface until high-pressure gas is saturated in the blank with the incompletely fused interface, foaming the blank with the incompletely fused interface by a pressure relief method or a heating method, forming cells at the interface of the blank with the incompletely fused interface, and shaping the cells to obtain the foaming material; temperature T 2 Selecting in a foaming temperature window common to the molded polymer blank A and the molded polymer blank B;
(3) Separating porous surfaces of polymers
Separating the foaming material from the incompletely fused interface of the foaming material obtained in the step (2), and simultaneously obtaining a polymer A with a porous structure on the surface and a polymer B with a porous structure on the surface;
the top of the surface porous structure of the polymer A with the surface porous structure and the polymer B with the surface porous structure is not covered by a cortex, and the surface porous structure is arranged in a single layer; the polymer A with the porous structure on the surface and the polymer B with the porous structure on the surface are respectively formed by converting a molded polymer blank A and a molded polymer blank B at two sides of an incompletely fused interface.
2. The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technology according to claim 1, wherein the molded polymer body A is prepared from an amorphous polymer, a crystalline polymer or a rubber with a crosslinking degree of 30% -60%, and the molded polymer body B is prepared from an amorphous polymer, a crystalline polymer or a rubber with a crosslinking degree of 30% -60%.
3. The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technique according to claim 2, wherein the molded polymer body A and the molded polymer body B are prepared from the polymer A and the polymer B, respectively, and the selected polymer and the fusion temperature T 1 And temperature T 2 The following requirements should be met:
fusion temperature T when shaped polymer body A and shaped polymer body B are made from the same amorphous polymer 1 Should satisfy T g -10℃≤T 1 ≤T g +30 ℃, temperature T 2 Should satisfy T g -70℃≤T 2 ≤T g +30℃，T g Is the glass transition temperature of the polymer;
when the shaped polymer body A and the shaped polymer body B are prepared from different amorphous polymers A and B, the glass transition temperatures of the polymers A and B should satisfy-30 ℃ T g Polymer A -T g Polymer B Let T be less than or equal to 30 DEG C g Polymer A ＞T g Polymer B Fusion temperature T 1 Should satisfy T g Polymer A -10℃≤T 1 ≤T g Polymer B +30 ℃, temperature T 2 Should satisfy T g Polymer A -70℃≤T 2 ≤T g Polymer B +30℃，T g Polymer A Is the glass transition temperature, T, of polymer A g Polymer B Is the glass transition temperature of polymer B;
fusion temperature T when shaped polymer body A and shaped polymer body B are made from the same crystalline polymer 1 Should satisfy T m -100℃≤T 1 ≤T m Temperature T 2 Should satisfy T m -100℃≤T 2 ≤T m ，T m Is the melting point of the polymer;
when the molded polymer body A and the molded polymer body B are prepared from different crystalline polymers A and B, the polymers A and B areThe melting point of B is less than or equal to-30 ℃ and less than or equal to T m Polymer A -T m Polymer B The temperature is less than or equal to 30 ℃; let T be m Polymer A ＞T m Polymer B Fusion temperature T 1 Should satisfy T m Polymer A -100℃≤T 1 ≤T m Polymer A Temperature T 2 Should satisfy T m Polymer A -100℃≤T 2 ≤T m Polymer A ，T m Polymer A T is the melting point of Polymer A m Polymer B Is the melting point of polymer B;
when the molding polymer body A and the molding polymer body B are respectively prepared from an amorphous polymer A and a crystalline polymer B, the glass transition temperature of the polymer A and the melting point of the polymer B should satisfy a temperature of-30 ℃ to T g Polymer A -T m Polymer B Let T be less than or equal to 30 DEG C g Polymer A ＞T m Polymer B Fusion temperature T 1 Should satisfy T g Polymer A -10℃≤T 1 ≤T g Polymer A +30 ℃, temperature T 2 Should satisfy T g Polymer A -70℃≤T 2 ≤T g Polymer A +30℃; let T be g Polymer A ＜T m Polymer B Fusion temperature T 1 Should satisfy T m Polymer B -100℃≤T 1 ≤T m Polymer B +30 ℃, temperature T 2 Should satisfy T m Polymer B -100℃≤T 2 ≤T m Polymer B +30℃；
When the molding polymer blank A and the molding polymer blank B are prepared from the same rubber, the crosslinking degree of the molding polymer blank A and the molding polymer blank B is between 30 and 60 percent, and the fusion temperature T is 1 The temperature is less than or equal to 0 ℃ and less than or equal to T 1 ≤T v Temperature T 2 The temperature is less than or equal to 0 ℃ and less than or equal to T 2 ≤T v ，T v Is the vulcanization temperature of rubber;
when the molding polymer blank A and the molding polymer blank B are prepared from different rubbers A and B, the crosslinking degree of the molding polymer blank A and the molding polymer blank B is between 30% and 60%, and the vulcanization temperature of the rubbers A and B is less than or equal to minus 30 ℃ and less than or equal to T vA -T vB The temperature is less than or equal to 30 ℃; let T be vA ＞T vB Fusion temperature T 1 The temperature is less than or equal to 0 ℃ and less than or equal to T 1 ≤T vB Temperature T 2 The temperature is less than or equal to 0 ℃ and less than or equal to T 2 ≤T vB ，T vA T is the vulcanization temperature of rubber A vB Is the vulcanization temperature of rubber B;
when the molded polymer body A is prepared from the polymer A and the polymer A is rubber, and the molded polymer body B is prepared from the amorphous or crystalline polymer B, the crosslinking degree of the molded polymer body A is between 30 and 60 percent, and the glass transition temperature T of the polymer B is between g Or melting point T m The temperature is less than or equal to 0 ℃ and less than or equal to (T) g Or T m )≤T v Fusion temperature T 1 Should satisfy (T) g Or T m )≤T 1 ≤T v Temperature T 2 Should satisfy (T) g Or T m )≤T 2 ≤T v ，T v Is the vulcanization temperature of polymer a.
4. The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technique according to claim 1, wherein at least one of the molded polymer bodies A and at least one of the molded polymer bodies B is used, and when the number of the molded polymer bodies A or B exceeds one, the molded polymer bodies A and B are alternately laminated at a fusion temperature T 1 Applying a fusion pressure P to the overlapped blanks 1 And (3) enabling the interface of the molded polymer blank A and the molded polymer blank B to be incompletely fused, so as to obtain a blank with incompletely fused interface.
5. The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technology according to claim 1, wherein the surfaces of the molded polymer body A and the molded polymer body B which are in contact with each other after lamination are flat surfaces or concave surfaces and convex surfaces which are matched with each other.
6. Surface structure of polymer according to any one of claims 1 to 5 using high pressure gas foaming technologyA method for constructing a skinnless porous structure, characterized in that the fusion pressure P 1 1-30 MPa.
7. The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technique as claimed in claim 6, wherein the method comprises the steps of at a fusion temperature T 1 Applying a fusion pressure P to the overlapped blanks 1 The duration of the process is 1 to 60 minutes.
8. The method of constructing a skinnless porous structure on a polymer surface using high pressure gas foaming technology according to any one of claims 1 to 5 wherein the shaped polymer body a and/or shaped polymer body B may further comprise a filler in an amount of not more than 50% of the mass of polymer in the shaped polymer body a or shaped polymer body B.
9. The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technique according to any one of claims 1 to 5, wherein the pore diameter and the surface roughness of the surface porous structure of the polymer a having a porous structure on the surface and the polymer B having a porous structure on the surface can be controlled by controlling the kind of the polymer in the green body with incompletely fused interfaces, the degree of fusion of the interfaces of the green body with incompletely fused interfaces, and the foaming conditions.
10. The method for constructing a skin-free porous structure on a polymer surface by using a high-pressure gas foaming technique according to claim 9, wherein the regulation range of pore diameters of the surface porous structures of the polymer A with the porous structure and the polymer B with the porous structure is 100 nm-100 μm, and the regulation range of surface roughness of the polymer A with the porous structure and the polymer B with the porous structure is 100 nm-20 μm.
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