CN111808259B - 3D printing silicone rubber and preparation method and application thereof - Google Patents
3D printing silicone rubber and preparation method and application thereof Download PDFInfo
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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Abstract
The invention belongs to the technical field of new materials, and provides 3D printing silicone rubber and a preparation method and application thereof, wherein the 3D printing silicone rubber mainly comprises amino or hydroxyl terminated polydimethylsiloxane, diisocyanate, an aminopyrazole compound, a cross-linking agent and a solvent, and the preparation method of the 3D printing silicone rubber comprises the following steps: dissolving amino or hydroxyl-terminated polydimethylsiloxane, diisocyanate, an aminopyrazole compound and a crosslinking agent in a solvent according to a certain mass part, stirring and reacting to obtain a prepolymer, adding the prepolymer into a mold after the reaction is finished, heating and curing, and removing the solvent to obtain the 3D printing silicone rubber material. The silicone rubber disclosed by the invention is good in mechanical strength and thermoplasticity, is suitable for printing products in various 3D printing and processing modes such as ink direct writing (DIW), fuse manufacturing (FFF), Selective Laser Sintering (SLS), ink-jet 3D printing (3DP) and the like, is non-toxic and harmless, has a self-repairing function, and is applied to the fields of flexible electronics, biomedicine and the like.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to 3D printing silicone rubber, and a preparation method and application thereof.
Background
The polysiloxane main chain is composed of silicon and oxygen atoms alternately, organic groups are directly connected to the silicon atoms, and the polysiloxane has the characteristics of inorganic and organic polymers, such as high and low temperature resistance, weather resistance, electrical insulation, ozone resistance, hydrophobicity, good gas permeability, no toxicity, biological inertia and the like. Is widely applied to the fields of electronics, electrics, buildings, automobiles, textiles, medical treatment and the like. Polysiloxane chains are flexible and have low intermolecular forces, and are therefore generally used in the form of crosslinked elastomers. The traditional silicon rubber product can only be manufactured by an injection molding process, and has the defects of high technical requirement on a mold, high cost, long processing period, low production efficiency, troublesome subsequent maintenance and the like, and can not produce silicon rubber products with precise structures and high precision.
Currently, silicone rubbers that can be used for 3D printing have been reported. Velind et al report a capillary ink 3D printed silicone rubber material. They prepared water with crosslinked polydimethylsiloxane microbeads and liquid non-crosslinked polydimethylsiloxane into multiphase inks. Because the micro beads can be combined through capillary action, the ink is paste, can flow under high shear stress and can be directly extruded and printed, but the mechanical property of the printed product is poor. Short conversation at Guangdong university etc. reported a highly transparent Digital Light Processing (DLP) printed silicone rubber. They use mercapto-olefinic bond reaction to realize the photocuring shaping of materials, and generate ionic interaction to strengthen the materials through carboxyl in the side chain of polydimethylsiloxane precursor and amino at high temperature. However, the strength of the material is only 0.23MPa, which severely restricts the application of the material. Most of 3D printed silicone rubber products reported at present adopt a photocuring forming mechanism, the printing method is single, the mechanical strength of the printed products is not high, and the residual photoinitiator also has potential biological toxicity.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a 3D printing silicone rubber and a preparation method and application thereof, wherein the pyrazole urea dynamic bond is obtained by reacting pyrazole and isocyanate, and is a novel thermal response type dynamic bond, so that a cross-linked silicone rubber material can be heated and flowed, has thermal processability, and can be used for various 3D printing processing modes such as heating ink direct writing, fuse wire manufacturing, selective laser sintering, ink-jet 3D printing, and the like, and the dynamic bond reaction enhances the interlayer of a self-repairing printed product, reduces the anisotropy of the mechanical strength of the product, enables the printed product to have a self-repairing function, enables the damage of the bonding force of the printed product to be completely repaired at 120 ℃, and improves the mechanical strength of the material, and the silicone rubber has excellent mechanical properties, the printing ink is suitable for various 3D printing modes, has a self-repairing function, and is simple in preparation process and relatively low in cost.
In order to achieve the above and other related objects, the invention provides a 3D printing silicone rubber, which comprises the following raw materials in parts by weight:
18-31 parts of amino or hydroxyl terminated polydimethylsiloxane, 10-41 parts of diisocyanate, 5-35 parts of aminopyrazole compound, 2-12 parts of cross-linking agent and 20-50 parts of solvent.
Preferably, the amino-terminated or hydroxyl-terminated polydimethylsiloxane is at least one of amino-terminated or hydroxyl-terminated polydimethylsiloxanes with molecular weights of 300-50000.
Preferably, the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, or dicyclohexylmethane diisocyanate.
Preferably, the aminopyrazole compound is 3-aminopyrazole, 2H-3-aminopyrazole, 3-amino-5-pyrazolol, 3, 5-diaminopyrazole, 3- (4-aminobenzene) -5-aminopyrazole, ethyl 5-amino-1H-pyrazole-4-carboxylate, 3-amino-4-cyanopyrazole, 3-amino-5-hydroxypyrazole, 3-amino-5-methylpyrazole, 5-amino-1H-pyrazole-3-acetic acid, 3-phenyl-1H-pyrazol-5-amine, 3- (3-bromophenyl) -5-aminopyrazole, 4-aminopyrazolo [3,4-d ] pyrimidine, 3-amino-5-tert-butylpyrazole, 3-aminopyrazole-4-carboxylic acid methyl ester, 3-aminopyrazole-4-carboxamide, 5-amino-3- (4-bromophenyl) -1H-pyrazole, or 4-aminopyrazole-5-carboxylic acid ethyl ester.
Preferably, the crosslinking agent is at least one of hexamethylene diisocyanate trimer, toluene diisocyanate trimer or isophorone diisocyanate trimer.
Preferably, the solvent is at least one of toluene, xylene, dichloromethane, chloroform, tetrahydrofuran or 1, 4-dioxane.
A preparation method of 3D printing silicone rubber mainly comprises the following steps:
the method comprises the following steps: weighing raw materials in proportion, dissolving the raw materials in a solvent to obtain a reaction solution, and stirring the reaction solution at room temperature for 2-10 hours to obtain a prepolymer;
step two: pouring the polymer obtained in the step one into a mold, putting the mold into an oven to remove the solvent, continuously curing, and taking out the mold after curing is finished to obtain a 3D printing silicone rubber solid containing the pyrazole urea dynamic bond;
step three: extruding the 3D printing silicon rubber solid obtained in the step two through a double-screw extruder, and cooling the air to obtain 3D printing silicon rubber strands containing pyrazole urea dynamic bonds;
step four: and D, crushing the 3D printing silicon rubber solid obtained in the step two by using a low-temperature crusher to obtain 3D printing silicon rubber powder containing the pyrazole urea dynamic bond.
Preferably, in the second step, the mold is a polytetrafluoroethylene mold, the temperature in the oven is 80 ℃, the time for removing the solvent from the prepolymer and continuously curing the prepolymer is 10-96 hours, and the solvent vapor of the prepolymer in the process of removing the solvent in the oven is recovered by a solvent recovery machine.
Preferably, in the third step, the extrusion temperature of the 3D printing silicone rubber solid in the double-screw extruder is 120-180 ℃.
The 3D printing silicone rubber solid containing the pyrazole urea dynamic key is applied to a 3D printing technology of a heating ink direct-writing melt, the 3D printing silicone rubber strand containing the pyrazole urea dynamic key is applied to a strand 3D printing technology for fuse wire manufacturing, the 3D printing silicone rubber powder containing the pyrazole urea dynamic key is applied to a 3D printing technology of selective laser sintering and inkjet 3D printing powder, and a printing product obtained by the 3D printing technology is applied to the fields of flexible electronics, biomedicine and the like.
As described above, the 3D printing silicone rubber, and the preparation method and the application thereof of the invention have the following beneficial effects:
in the invention, the amino pyrazole compound in the raw materials enables the molecular weight main chain to be provided with the polyurea chain segment, so that the mechanical strength of the material can be obviously improved, and the tensile strength can reach 7 MPa.
According to the invention, the pyrazole urea bond in the 3D printing silicone rubber containing the pyrazole urea dynamic bond is a thermally reversible chemical bond, and can be broken at high temperature, and can be regenerated after the temperature is reduced, so that the prepared cross-linked silicone rubber has a processable property, is suitable for various 3D printing processing modes, and can be applied to the fields of flexible electronics, biomedicine and the like.
According to the invention, the 3D printing silicone rubber containing the pyrazole urea dynamic bond has self-repairability, and the 3D printing product can realize damage repair without any additional repairing agent or catalyst.
In the invention, the used raw materials are easy to obtain, the synthesis process is simple and easy to control, and the yield is high.
Drawings
Fig. 1 is a chemical structure of 3D printing silicone rubber containing a pyrazole urea dynamic bond prepared in experimental example 2;
FIG. 2 is an infrared spectrum of 3D printed silicone rubber containing a pyrazolea dynamic bond prepared in test example 2;
FIG. 3 is a drawing of a 3D printed silicone rubber solid containing pyrazole urea dynamic bonds in test example 2;
FIG. 4 is a Scanning Electron Microscope (SEM) image of 3D printed silicone rubber powder containing pyrazolea dynamic bonds in test example 2;
FIG. 5 is a drawing of a 3D printed silicone rubber tensile bar containing a pyrazole urea dynamic bond in test example 4;
FIG. 6 is a drawing of a 3D printed silicone rubber orthopedic insole containing a pyrazolea dynamic bond in test example 4;
FIG. 7 is a stress-strain curve graph before and after damage repair of 3D printed silicone rubber printed tensile sample strips containing pyrazolea dynamic bonds in test example 5;
FIG. 8 is a real object diagram before and after repairing damage of a 3D printed silicon rubber printed insole containing a pyrazole urea dynamic key in test example 5;
FIG. 9 is a schematic view of solid particles of silicone rubber containing pyrazolea dynamic bonds in test example 3;
FIG. 10 is a schematic view of non-dynamic comparative silicone rubber solid particles containing a general urea bond in test example 3;
fig. 11 is a schematic view of solid silicone rubber particles containing a pyrazole urea dynamic bond in test example 3 after hot press molding;
FIG. 12 is a schematic view of non-dynamic comparative silicone rubber solid particles containing a general urea bond in test example 3 after hot press molding.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Example 1
The 3D printing silicone rubber comprises 2-12 parts of a cross-linking agent, 18-31 parts of amino or hydroxyl terminated polydimethylsiloxane, 10-41 parts of diisocyanate, 5-35 parts of an aminopyrazole compound and 20-50 parts of a solvent.
The preparation method of the 3D printing silicone rubber comprises the following steps:
the method comprises the following steps: weighing 2-12 parts of a cross-linking agent, 18-31 parts of amino or hydroxyl terminated polydimethylsiloxane, 10-41 parts of diisocyanate, 5-35 parts of an aminopyrazole compound and 20-50 parts of a solvent according to a proportion, dissolving the raw materials in the solvent to obtain a reaction solution, and stirring and reacting at room temperature for 2-10 hours to obtain a prepolymer;
step two: pouring the polymer obtained in the step one into a mold, putting the mold into an oven at 80 ℃ to remove the solvent, continuously curing for 10-96 hours, recovering solvent steam through a solvent recovery machine, and taking out the mold after curing to obtain 3D printing silicone rubber solid containing the pyrazole urea dynamic bond;
step three: extruding the 3D printing silicon rubber solid obtained in the step two at the temperature of 120-180 ℃ through a double-screw extruder, and cooling the air to obtain 3D printing silicon rubber strands containing the pyrazole urea dynamic bond;
step four: and D, crushing the 3D printing silicon rubber solid obtained in the step two by using a low-temperature crusher to obtain 3D printing silicon rubber powder containing the pyrazole urea dynamic bond.
Wherein the amino-terminated or hydroxyl-terminated polydimethylsiloxane is at least one of amino-terminated or hydroxyl-terminated polydimethylsiloxane with the molecular weight of 300-50000.
The diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
The aminopyrazole compound is 3-aminopyrazole, 2H-3-aminopyrazole, 3-amino-5-pyrazolol, 3, 5-diaminopyrazole, 3- (4-aminobenzene) -5-aminopyrazole, 5-amino-1H-pyrazole-4-carboxylic acid ethyl ester, 3-amino-4-cyanopyrazole, 3-amino-5-hydroxypyrazole, 3-amino-5-methylpyrazole, 5-amino-1H-pyrazole-3-acetic acid, 3-phenyl-1H-pyrazole-5-amine, 3- (3-bromophenyl) -5-aminopyrazole, 4-aminopyrazolo [3,4-d ] pyrimidine, pyridine, or pyridine, 3-amino-5-tert-butylpyrazole, 3-aminopyrazole-4-carboxylic acid methyl ester, 3-aminopyrazole-4-carboxamide, 5-amino-3- (4-bromophenyl) -1H-pyrazole, 4-aminopyrazole-5-carboxylic acid ethyl ester.
The crosslinking agent is at least one of hexamethylene diisocyanate trimer, toluene diisocyanate trimer and isophorone diisocyanate trimer.
The solvent is at least one of toluene, xylene, dichloromethane, chloroform, tetrahydrofuran and 1, 4-dioxane.
In the embodiment, the obtained pyrazole urea bond-containing silicone rubber solid is applied to melt 3D printing technologies such as heating ink direct writing and the like, strand is applied to strand 3D printing technologies such as fuse manufacturing and the like, powder is applied to powder 3D printing technologies such as selective laser sintering and inkjet 3D printing and the like, and a printed product is applied to the fields of flexible electronics, biomedicine and the like.
Example 2
5.4g aminopropyl terminated polydimethylsiloxane DMS-A15, 0.532g isophorone diisocyanate, 0.1g 3-amino-5-tert-butylpyrazole and 0.2g hexamethylene diisocyanate trimer were dissolved in 20ml tetrahydrofuran, the mixture was stirred at room temperature for 3 hours to react to obtain a prepolymer, the prepolymer obtained by the reaction was poured into a polytetrafluoroethylene mold, and then put into an oven at 80 ℃ for further curing for 24 hours, and then taken out of the mold to obtain a silicone rubber solid containing a pyrazole urea dynamic bond, the chemical structures of the raw materials and the synthetic silicone rubber are shown in FIG. 1, the obtained silicone rubber was subjected to infrared spectrum detection, the detection result is shown in FIG. 2, and the real object is shown in FIG. 3. Fig. 4 shows a powder obtained by pulverizing a silicone rubber solid in a low-temperature pulverizer.
As can be seen from the figure: the silicon rubber is a chemical crosslinking structure, and the characteristic peak (2240) -2280 cm-1) of an isocyanate group in an infrared spectrum disappears, so that the components are completely reacted. In fig. 1, R ═ H, CH 3, and C (CH 3) 3. The particle size of the powder after low-temperature grinding is about 100-200 mu m, and the requirement of selective laser sintering 3D printing is met.
Example 3
5.4g of aminopropyl-terminated polydimethylsiloxane DMS-A15, 0.532g of isophorone diisocyanate, 0.08g of p-phenylenediamine and 0.2g of hexamethylene diisocyanate trimer are dissolved in 20ml of tetrahydrofuran, the mixture is stirred at room temperature for reaction for 3 hours, after the reaction is finished, the prepolymer is poured into a polytetrafluoroethylene mold, and then the polytetrafluoroethylene mold is placed into an oven at 80 ℃ for continuous curing for 24 hours, and then the prepolymer is taken out of the mold to obtain the non-dynamic contrast silicone rubber solid containing the common urea bond.
The silicone rubber solid containing a pyrazole urea dynamic bond obtained in example 2 (shown in fig. 9) and the non-dynamic comparative silicone rubber solid containing a general urea bond obtained in example 3 (shown in fig. 10) were hot-press molded at 120 ℃ and 10MPa, respectively, for 30 minutes, and the shapes of the hot-press molded silicone rubber solid containing a pyrazole urea dynamic bond and the non-dynamic comparative silicone rubber solid containing a general urea bond were shown in fig. 11 and 12, respectively.
As can be seen from fig. 9 to 12, the silicone rubber solid particles containing pyrazole urea dynamic bonds have dynamic properties, and the solid particles can be hot-pressed and reprocessed, whereas the non-dynamic comparative silicone rubber solid particles containing ordinary urea bonds have no dynamic properties, and the solid particles cannot be hot-pressed and reprocessed.
In conclusion, the pyrazole urea bond formed by the reaction of the aminopyrazole and the isocyanate has dynamic property, can be dissociated at high temperature and can be regenerated at low temperature. The dynamic cross-linking structure formed by the dynamic bond enables the silicon rubber material to be thermally processed by means of 3D printing, hot pressing and the like, but common non-dynamic silicon rubber does not have the performance.
Example 4
3D printing silicon rubber printing product display containing pyrazole urea dynamic bond: the silicone rubber powder prepared in test example 2 (shown in fig. 4) was used for Selective Laser Sintering (SLS)3D printing with the following printing parameters: the powder bed temperature is 70 ℃, the laser power is 60W, and the scanning distance is 0.08 mm. The 3D printed tensile spline is shown in fig. 5 and the 3D printed orthopedic insole is shown in fig. 6.
As can be seen from the figure: the 3D printing silicone rubber containing the pyrazole urea dynamic bond has the processibility, is suitable for 3D printing, and can be used for printing out required products according to requirements.
Example 5
The self-repairing performance display of the 3D printing silicone rubber printing product containing the pyrazole urea dynamic bond comprises the following steps: the 3D printed silicone rubber sample necks of test example 4 were cut with a razor blade and then placed in a 120 c oven for 1 hour with both end faces attached together and then in an 80c oven for 6 hours with the test results shown in figure 7. The 3D printed orthopedic insoles of test example 4 were cut with a razor blade, aligned and the insoles were placed together in an oven at 120 c for 1 hour and then in an oven at 80c for 6 hours, the test results are shown in fig. 8, fig. 8 is a comparison of the orthopedic insoles before and after repair.
The pyrazole urea dynamic bond is obtained by reacting pyrazole and isocyanate, is a novel thermal response type dynamic bond, enhances the interlayer bonding force of the printed product, reduces the anisotropy of the mechanical strength of the product, enables the printed product to have a self-repairing function, and can completely repair the damage of the product at 120 ℃.
As can be seen from fig. 7, the stress-strain curves before and after the 3D printed silicone rubber sample bar neck containing the pyrazole urea dynamic bond was cut with the blade were the same, and thus it was found that the 3D printed silicone rubber containing the pyrazole urea dynamic bond had self-repairability, and the 3D printed product could achieve damage repair without any additional repair agent or catalyst.
As can be seen from fig. 8, the 3D printed orthopedic insole containing the pyrazole urea dynamic bond has no cut after the cut is scribed by the blade for repair, and completely recovers the state before the cut, so that the 3D printed silicone rubber containing the pyrazole urea dynamic bond has self-repairability, and the 3D printed product can realize damage repair without any additional repair agent or catalyst.
Meanwhile, the pyrazole urea dynamic bond obtained by the reaction of pyrazole and isocyanate can improve the mechanical strength of the material, and as can be seen from the origin curve in fig. 7, the tensile strength of the 3D printing silicone rubber containing the pyrazole urea dynamic bond in the application can reach 7MPa, and compared with the strength of a 3D printing silicone rubber material in the prior art which is only 0.23MPa, the tensile strength of the material is obviously improved.
In conclusion, the 3D printed silicone rubber containing the pyrazole urea dynamic bond has the same shape after being cut and repaired and the same stress-strain curve before being cut, and thus, the 3D printed silicone rubber containing the pyrazole urea dynamic bond has self-repairing property, and the 3D printed product can realize damage repair without any external repairing agent or catalyst.
In conclusion, the pyrazole urea dynamic bond is obtained by reacting pyrazole and isocyanate, is a novel thermal response type dynamic bond, can enable a cross-linked silicone rubber material to be heated and flow, has thermal processability, can be used for various 3D printing processing modes such as heating ink direct writing, fuse wire manufacturing, selective laser sintering, ink-jet 3D printing and the like, simultaneously enhances the interlayer bonding force of the printed product and reduces the anisotropy of the mechanical strength of the product through the dynamic bond reaction, enables the printed product to have a self-repairing function, enables the damage of the product to be completely repaired at 120 ℃, and also improves the mechanical strength of the self-repairing material. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. The 3D printing silicone rubber is characterized by comprising the following raw materials in parts by weight:
18-31 parts of amino or hydroxyl terminated polydimethylsiloxane, 10-41 parts of diisocyanate, 5-35 parts of aminopyrazole compound, 2-12 parts of cross-linking agent and 20-50 parts of solvent, wherein the aminopyrazole compound is 3-aminopyrazole, 2H-3-aminopyrazole, 3-amino-5-pyrazole alcohol, 3, 5-diaminopyrazole, 3- (4-aminobenzene) -5-aminopyrazole, 5-amino-1H-pyrazole-4 ethyl carboxylate, 3-amino-4-cyanopyrazole, 3-amino-5-methylpyrazole, 5-amino-1H-pyrazole-3-acetic acid, 3-phenyl-1H-pyrazole-5-amine, 3-amino-5-amino-pyrazole, 3- (3-bromophenyl) -5-aminopyrazole, 4-aminopyrazolo [3,4-d ] pyrimidine, 3-amino-5-tert-butylpyrazole, 3-aminopyrazole-4-carboxylic acid methyl ester, 3-aminopyrazole-4-carboxamide, 5-amino-3- (4-bromophenyl) -1H-pyrazole, or 4-aminopyrazole-5-carboxylic acid ethyl ester, and the crosslinking agent is at least one of hexamethylene diisocyanate trimer, toluene diisocyanate trimer, or isophorone diisocyanate trimer.
2. The 3D printing silicone rubber according to claim 1, wherein: the amino-terminated or hydroxyl-terminated polydimethylsiloxane is at least one of amino-terminated or hydroxyl-terminated polydimethylsiloxane with the molecular weight of 300-50000.
3. The 3D printing silicone rubber according to claim 1, wherein: the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate or dicyclohexylmethane diisocyanate.
4. The 3D printing silicone rubber according to claim 1, wherein: the solvent is at least one of toluene, xylene, dichloromethane, chloroform, tetrahydrofuran or 1, 4-dioxane.
5. The preparation method of the 3D printing silicone rubber according to any one of claims 1 to 4, wherein the preparation method comprises the following steps: the method mainly comprises the following steps:
the method comprises the following steps: weighing raw materials in proportion, dissolving the raw materials in a solvent to obtain a reaction solution, and stirring the reaction solution at room temperature for 2-10 hours to obtain a prepolymer;
step two: pouring the prepolymer obtained in the step one into a mold, putting the mold into an oven to remove the solvent, continuously curing, and taking out the mold after curing is finished to obtain a 3D printing silicone rubber solid containing the pyrazole urea dynamic bond;
step three: extruding the 3D printing silicon rubber solid obtained in the step two through a double-screw extruder, and cooling the air to obtain 3D printing silicon rubber strands containing pyrazole urea dynamic bonds; or the like, or, alternatively,
step four: and D, crushing the 3D printing silicon rubber solid obtained in the step two by using a low-temperature crusher to obtain 3D printing silicon rubber powder containing the pyrazole urea dynamic bond.
6. The preparation method of the 3D printing silicone rubber according to claim 5, wherein the preparation method comprises the following steps: in the second step, the mold is a polytetrafluoroethylene mold, the temperature in the oven is 80 ℃, the time for removing the solvent from the prepolymer and continuously curing the prepolymer is 10-96 hours, and the solvent steam of the prepolymer in the process of removing the solvent in the oven is recovered by a solvent recovery machine.
7. The preparation method of the 3D printing silicone rubber according to claim 5, wherein the preparation method comprises the following steps: in the third step, the extrusion temperature of the 3D printing silicone rubber solid in the double-screw extruder is 120-180 ℃.
8. The application of the 3D printing silicone rubber prepared by the preparation method of the 3D printing silicone rubber according to claim 5, wherein the preparation method comprises the following steps: the 3D printing silicone rubber solid containing the pyrazole urea dynamic key is applied to a 3D printing technology of a heating ink direct-writing melt, the 3D printing silicone rubber strand containing the pyrazole urea dynamic key is applied to a 3D printing technology of fuse manufacturing strands, the 3D printing silicone rubber powder containing the pyrazole urea dynamic key is applied to a 3D printing technology of selective laser sintering and ink-jet 3D printing powder, and a printing product obtained by the 3D printing technology is applied to the fields of flexible electronics and biomedicine.
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