阅读说明：本技术 一种基于形状记忆效应的溶胀聚合温控电路的制备方法及电路装置 (Preparation method of swelling polymerization temperature control circuit based on shape memory effect and circuit device ) 是由 吴雪莲 姜江 曹明昊 郭玉琴 徐凡 袁晓明 于 2019-08-30 设计创作，主要内容包括：本发明公开了一种基于形状记忆效应的溶胀聚合温控电路的制备方法及电路装置,涉及温控电路领域,基体为绝缘形状记忆聚合物,在基体表面加工出连续的凹陷结构,所述凹陷区域的深度不大于基体材料厚度的三分之二；所述凹陷结构的深度可相同,也可不同；所述凹陷结构可以是在基体表面加工出的凹槽结构,也可以是在特定温度下进行压印预变形处理所制备的凹痕结构；在凹陷结构中引入有机溶剂,使得有机溶剂和凹陷区域材料发生一定深度范围的溶胀；在凹陷的溶胀区域引入可形成导电物质的溶液；所述导电物质的溶液进入溶胀区材料分子链段形成的网络空隙为反应池,生成导电物质；对溶胀氧化聚合完的凹陷区域固化处理后得到导电线路。(The invention discloses a preparation method of a swelling polymerization temperature control circuit based on a shape memory effect and a circuit device, and relates to the field of temperature control circuits, wherein a substrate is an insulating shape memory polymer, a continuous concave structure is processed on the surface of the substrate, and the depth of a concave area is not more than two thirds of the thickness of a substrate material; the depths of the concave structures can be the same or different; the concave structure can be a groove structure processed on the surface of the substrate or a dent structure prepared by carrying out stamping pre-deformation treatment at a specific temperature; introducing an organic solvent into the recessed structure, so that the organic solvent and the recessed area material are swelled within a certain depth range; introducing a solution capable of forming a conductive substance into the swollen region of the recess; the solution of the conductive substance enters a network gap formed by the molecular chain segment of the material in the swelling area to be a reaction pool, and the conductive substance is generated; and curing the swelled, oxidized and polymerized concave area to obtain the conductive circuit.)

1. A preparation method of a swelling polymerization temperature control circuit based on a shape memory effect is characterized in that,

(a) the substrate is an insulating shape memory polymer;

(b) processing a continuous concave structure on the surface of the substrate, wherein the depth of the concave structure is not more than two thirds of the thickness of the substrate material; the concave structure is a groove structure processed on the surface of the substrate or a dent structure prepared by carrying out impression pre-deformation treatment at a specific temperature;

(c) introducing an organic solvent into the recessed structure, so that the organic solvent and the recessed area material are swelled within a certain depth range;

(d) introducing a solution capable of forming a conductive substance into the swollen region of the recess; the solution of the conductive substance enters a network gap formed by the molecular chain segment of the material in the swelling area to be a reaction pool, and the conductive substance is generated; and curing the swelled, oxidized and polymerized concave area to obtain the conductive circuit embedded in a certain depth.

2. The method for preparing a swelling polymerization temperature control circuit based on shape memory effect according to claim 1,

(a) the substrate of the circuit is an insulating shape memory polymer;

(b) processing a linear groove structure on the surface of the substrate, dripping aniline solution into the dent area, and swelling aniline and the dent area material within a certain depth range; the depth of the swelled dent is not more than two thirds of the base material;

(c) dropping an oxidant into the swelled dent area to enable the oxidant to enter the molecular network gaps of the dent swelling area part of the shape memory polymer, and carrying out in-situ polymerization reaction on the aniline and the oxidant in the molecular network gaps of the swelled polymer to generate the conductive polyaniline;

(d) and curing the swelled, oxidized and polymerized dent area to obtain the conductive circuit embedded in a certain depth.

3. The method for preparing a temperature controlled polymerization circuit based on shape memory effect according to any one of claims 1 and 2, wherein the conductive substance has a conductivity in the range of 10^-5S/cm～10³S/cm。

4. The method for preparing a temperature-controlled polymerization circuit based on shape memory effect according to any one of claims 1 and 2, wherein the recessed structure can be a permanent groove structure realized by mechanical processing, or an indentation structure after imprinting pre-deformation treatment based on polymer shape memory effect; when the concave structure is realized by carrying out stamping pre-deformation treatment on the shape memory polymer substrate, the recovery temperature of the prepared pre-deformation dent for controlling the on-off of the circuit is lower than the shape recovery temperature of the first pre-deformation.

5. The method for preparing a temperature-controlled polymerization circuit based on shape memory effect according to any one of claims 1 and 2, wherein the pre-deformation treatment for making the conductive circuit non-conductive can be a strip-shaped local stamping perpendicular to the direction of the conductive circuit or a local stretching along the direction of the conductive circuit.

6. The method for preparing a temperature-controlled polymerization circuit based on shape memory effect according to claim 4, wherein when the recess structure is realized by pre-deforming the shape memory polymer substrate by stamping, the conductive circuit is heated to recover the shape of the pre-deformed portion, and the shape recovery rate is greater than 80%.

7. The method for preparing a temperature-controlled polymerization circuit based on the shape memory effect according to any one of claims 1 and 2, wherein the solution capable of forming the conductive substance can be one or more of graphene, carbon nanotubes, carbon powder and ketjen black, and can also be raw material monomers of polyaniline, polypyrrole, polyacetylene, polythiophene, polystyrene sulfonic acid and polyphenylene sulfide.

8. The method for preparing a temperature-controlled polymer circuit based on shape memory effect according to any one of claims 1 and 2, wherein the swelling treatment is performed on the polymer by using organic solvent. The organic solvent may be one or more of aniline, toluene, xylene, acetone, ethanol, dimethylformamide, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, dichloroethane, ethyl acetate, glycerol, triethanolamine, ethylenediamine, dichlorobenzene and ethylene glycol ether.

9. The method for preparing a temperature-controlled polymer circuit based on shape memory effect according to any one of claims 1 and 2, wherein the polymer is one or more of ethylene-vinyl acetate copolymer, polyurethane, polylactic acid, polycaprolactone, polytetrafluoroethylene, epoxy, polyimide, polycarbonate, phenolic resin, polymethyl methacrylate, polyphenylene oxide, cyanate ester, polyolefin, and polyaryletherketone.

10. The circuit device obtained by the method for preparing a swelling polymerization temperature control circuit based on shape memory effect according to any one of claims 1 and 2,

connecting the conductive circuits obtained in the step d through an electronic device to form a circuit device;

pre-deforming one or more sections of the conductive circuit at a specific temperature, so that the continuity of the conductive substance on the substrate is lost, and the circuit device is not connected; or the auxiliary agent is introduced into the deeper part of the surface of the concave structure with continuous and different depths, so that the conductive material loses the conductivity, the conductive circuit loses the continuous type, and the circuit device is not communicated;

heating the pre-deformation area in sequence, recovering the shape of the pre-deformation area, reforming the conductive substance into a continuous phase, and communicating the circuit device; or the auxiliary agent is introduced again, so that the non-conductive area has the conductive property again.

Technical Field

The invention relates to the field of temperature control circuits, in particular to a preparation method of a swelling polymerization temperature control circuit based on a shape memory effect and a circuit device.

Background

The current temperature control circuit technology mainly adopts a closed-loop control system, converts actual temperature parameters of a circuit into electric signals by a sensor, compares the electric signals with preset values for feedback, transmits feedback information to a controller, and then realizes the on-off of the circuit. Although the technology is widely applied, the equipment cost is high, certain response time is needed for working signal conversion and contrast feedback, and the on-off of the control circuit can be realized only by processing and feeding back signals by an external device. Therefore, the method has certain significance for the improvement and development of the temperature control circuit technology.

The shape memory polymer is a novel intelligent material, can have the function of keeping a temporary shape after being pre-deformed under different external stimulation conditions (heat, electricity, light and the like), and can automatically recover the original shape when being subjected to external stimulation again. The function can be applied to the on-off of the temperature control circuit, the self-recovery characteristic can be used as a controller of the circuit, and signal conversion and feedback response are not needed. The temperature control circuit is widely applied to household appliances such as refrigerators, washing machines, electric water heaters and the like, but the traditional temperature control circuit has the defects of complex structure, high cost, inconvenience in maintenance and the like, and cannot normally work in an electromagnetic environment, so that the application and development of the temperature control circuit are limited. The shape memory polymer has the characteristics of low cost, easiness in forming, portability, low requirement on working environment and the like, can be used as a substrate of a circuit to realize the on-off of the circuit, and has excellent prospect for the research and development and application of a temperature control circuit.

At present, related patents exist for the temperature control circuit technology, but certain defects exist. Chinese patent CN108321010A discloses a bidirectional temperature control switch system and method based on shape memory polymer, which is simple and convenient compared with the traditional temperature control circuit, but has certain disadvantages. Firstly, the conductive substance of the contact of the switch is coated with a carbon paste layer, the conductive layer is easy to fall off after multiple deformations, and the working stability is to be improved; secondly, the matrix preparation of the temperature control switch needs to add shape memory polymer fiber for hot press molding, and the preparation cost is high.

Patent CN204291556U discloses a rapidly changeable conductive component for circuits, which is based on shape memory polymer, and is prepared by pre-deforming a substrate and spraying or printing a conductive layer on the surface of the substrate. The patent requires that the initial shape of the surface of the substrate is a concave-convex structure, and the substrate is of a planar structure after pre-deformation, so that the requirement on the initial shape of the surface of the substrate is high, and the manufacturing cost is increased; secondly, the conducting layer of the circuit is sprayed or printed with conducting substances, so that the adhesion with the substrate is not high, and the service life and the stability are to be improved.

The patent CN107249254A discloses a stretchable or bendable composite circuit system and a preparation method thereof, wherein different hot melt adhesive components are added into an elastomer, an elastic shape memory polymer is prepared by molding through a mold, then certain stretching pre-deformation is carried out on the elastic shape memory polymer within a specific temperature range, and then the circuit system is sprayed, adhered or printed on the surface of a pre-deformed substrate. The matrix performance of the patent needs to add quantitative hot melt adhesive to prepare elastic shape memory polymers with different parameters, the manufacturing process is complex, and the equipment cost is high; the circuit system is adhered to the substrate in a spraying, pasting or printing mode, and the circuit stability and the service life are the defects; after the predeformation and restoration, the circuit forms wrinkles, which may cause the circuit to partially overlap and contact, and may have a certain influence on the normal operation of the circuit.

Disclosure of Invention

The invention provides a preparation method of a swelling polymerization temperature control circuit based on a shape memory effect and a circuit device, aiming at solving the technical problems of complex technology, high cost, limited working range and the like of the current temperature control circuit.

Compared with the prior art, the method has the advantages that the matrix with the shape memory effect is subjected to pre-deformation treatment and can be processed into the circuit structure which is switched on and off by the shape memory effect control circuit, so that the organic solvent and the matrix material are swelled in the processed circuit structure, the polymer molecular network gap formed by swelling is taken as a reaction pool to generate the conductive polymer through the in-situ polymerization reaction of the conductive polymer, the conductive function of the circuit is realized, and the switching on and off of the circuit is controlled through the shape memory effect.

Swelling polymerization temperature control circuit based on shape memory effect and preparation method thereof

(a) The substrate is an insulating shape memory polymer;

(b) processing a continuous concave structure on the surface of the substrate, wherein the depth of the concave region is not more than two thirds of the thickness of the substrate material; the depths of the concave structures can be the same or different; the concave structure can be a groove structure processed on the surface of the substrate or a dent structure prepared by carrying out stamping pre-deformation treatment at a specific temperature;

(c) introducing an organic solvent into the recessed structure, so that the organic solvent and the recessed area material are swelled within a certain depth range;

(d) introducing a solution capable of forming a conductive substance into the swollen region of the recess; the solution of the conductive substance enters a network gap formed by the molecular chain segment of the material in the swelling area to be a reaction pool, and the conductive substance is generated; and curing the swelled, oxidized and polymerized concave area to obtain the conductive circuit.

Further, (a) the substrate of the circuit is an insulating shape memory polymer;

(b) processing a linear groove structure on the surface of the substrate, dripping aniline solution into the dent area, and swelling aniline and the dent area material within a certain depth range; the depth of the swelled dent is not more than two thirds of the base material;

(c) dropping an oxidant into the swelled dent area to enable the oxidant to enter the molecular network gaps of the dent swelling area part of the shape memory polymer, and carrying out in-situ polymerization reaction on the aniline and the oxidant in the molecular network gaps of the swelled polymer to generate the conductive polyaniline; and curing the dent area after swelling, oxidizing and polymerizing to obtain the conductive circuit.

Further, the conductive substance has a conductivity ranging from 10^-5S/cm～10³S/cm。

Further, the linear concave structure can be a permanent concave structure realized by mechanical processing, and can also be an imprinting pre-deformation treatment based on a polymer shape memory effect.

Further, the pre-deformation process for making the conductive circuit non-conductive may be a strip-shaped local stamping perpendicular to the direction of the conductive circuit, or a local stretching along the direction of the conductive circuit.

Further, when the concave structure is realized by carrying out imprinting pre-deformation treatment on the shape memory polymer substrate, the temperature of the pre-deformation treatment for carrying out non-connection of the conductive circuit is lower than that of the first imprinting pre-deformation treatment.

Furthermore, when the concave structure is realized by carrying out imprinting pre-deformation treatment on the shape memory polymer substrate, the concave structure can be heated after the conductive circuit is prepared, so that the shape of the concave structure is recovered, and the shape recovery rate is more than 80%.

Further, the solution capable of forming the conductive substance may be a dispersion liquid formed by one or more of graphene, carbon nanotubes, carbon powder and ketjen black in an organic solution, and may also be a raw material monomer of polyaniline, polypyrrole, polyacetylene, polythiophene, polystyrene sulfonic acid and polyphenylene sulfide.

Further, the swelling treatment is carried out on the polymer using an organic solvent. The organic solvent may be one or more of aniline, toluene, xylene, acetone, ethanol, dimethylformamide, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, dichloroethane, ethyl acetate, glycerol, triethanolamine, ethylenediamine, dichlorobenzene and ethylene glycol ether.

Further, the polymer is one or more of ethylene-vinyl acetate copolymer, polyurethane, polylactic acid, polycaprolactone, polytetrafluoroethylene, epoxy, polyimide, polycarbonate, phenolic resin, polymethyl methacrylate, polyphenyl ether, cyanate ester, polyolefin and polyaryletherketone.

A circuit device obtained by the preparation method of the swelling polymerization temperature control circuit based on the shape memory effect,

the method comprises the following steps: connecting the conductive circuits obtained in the step d through an electronic device to form a circuit device;

step two: pre-deforming one or more sections of the conductive circuit at a specific temperature, so that the continuity of the conductive substance on the substrate is lost, and the circuit device is not connected; or the auxiliary agent is introduced into the deeper part of the surface of the concave structure with continuous and different depths, so that the conductive material loses the conductivity, the conductive circuit loses the continuous type, and the circuit device is not communicated;

step three: heating the pre-deformation area in sequence, recovering the shape of the pre-deformation area, reforming the conductive substance into a continuous phase, and communicating the circuit device; or the auxiliary agent is introduced again, so that the non-conductive area has the conductive property again.

Compared with the prior art, the invention has the following advantages:

1. according to the preparation method of the swelling polymerization temperature control circuit based on the shape memory effect, the conductive circuit is a conductive substance which is polymerized in the swelling area with a certain depth, so that the conductive circuit and the substrate have good connectivity.

2. According to the preparation method of the swelling polymerization temperature control circuit based on the shape memory effect, the conductive components in the conductive circuit exist in polymer molecular network gaps formed by swelling, and the polymer molecular network gaps are in a reaction pool, so that the influence of air environment factors is small, and the conductivity is stable.

3. According to the preparation method of the swelling polymerization temperature control circuit based on the shape memory effect, the on-off of the control circuit is controlled without signal conversion and feedback, and the on-off of the circuit is controlled by controlling the change of temperature (controlling the occurrence of the shape memory effect) or dropwise adding a specific solvent in a local circuit area.

4. According to the preparation method of the swelling polymerization temperature control circuit based on the shape memory effect, the control circuit can control the on-off of the circuit in different areas at a specific temperature.

5. The preparation method of the swelling polymerization temperature control circuit based on the shape memory effect has the advantages of simple circuit swelling polymerization scheme, low requirement on equipment, simple and convenient process, high efficiency and economy.

6. According to the preparation method of the swelling polymerization temperature control circuit based on the shape memory effect, the whole matrix is made of the shape memory polymer, and the preparation method can be applied to related foldable circuits.

Drawings

FIG. 1(a) is a schematic structural diagram of a conductive polymer (grey is conductive polymer) formed by swelling and polymerization after processing a linear groove on the surface of a substrate according to an embodiment of the present invention;

FIG. 1(b) is a schematic structural diagram of a conductive polymer in a linear groove after pre-deformation treatment (gray is conductive polymer) according to an embodiment of the present invention;

fig. 1(c) is a schematic structural diagram illustrating a thermal recovery of a conductive circuit after pre-deformation according to an embodiment of the invention;

FIG. 2(a) is a schematic structural diagram of grooves with different depths formed on the surface of a substrate by pre-deformation processing in the third embodiment of the present invention;

fig. 2(b) is a schematic structural diagram of a discontinuous conductive circuit by dropping an auxiliary agent in the third embodiment of the present invention (black is a non-conductive substance);

fig. 2(c) is a schematic structural diagram of a conductive line made continuous by adding an auxiliary agent in the third embodiment of the present invention;

FIG. 3(a) is a schematic diagram of a line-shaped groove machined on the surface of a substrate according to an eighth embodiment of the present invention;

FIG. 3(b) is a schematic structural diagram of swelling polymerization into a continuous conductive polymer in linear grooves in example eight of the present invention (grey is conductive polymer);

fig. 3(c) is a schematic structural diagram of a circuit discontinuously losing conductivity after the whole conductive circuit is transversely stretched in an eighth embodiment of the invention (black is a non-conductive portion, and gray is a conductive polymer);

fig. 3(d) is a schematic circuit structure diagram after recovery after pre-stretching deformation in the eighth embodiment of the present invention;

FIG. 4 is a flow chart of the present invention technique.

Detailed Description