CN116813865A - 3D printing self-repairing silicone rubber and preparation method thereof - Google Patents
3D printing self-repairing silicone rubber and preparation method thereof Download PDFInfo
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- CN116813865A CN116813865A CN202310879840.9A CN202310879840A CN116813865A CN 116813865 A CN116813865 A CN 116813865A CN 202310879840 A CN202310879840 A CN 202310879840A CN 116813865 A CN116813865 A CN 116813865A
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 69
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 63
- 238000010146 3D printing Methods 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 34
- -1 polydimethylsiloxane, diisocyanate Polymers 0.000 claims abstract description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 12
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000013638 trimer Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ICFJFFQQTFMIBG-UHFFFAOYSA-N phenformin Chemical compound NC(=N)NC(=N)NCCC1=CC=CC=C1 ICFJFFQQTFMIBG-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims description 2
- 229960003105 metformin Drugs 0.000 claims description 2
- 229960003243 phenformin Drugs 0.000 claims description 2
- CUQCMXFWIMOWRP-UHFFFAOYSA-N phenyl biguanide Chemical compound NC(N)=NC(N)=NC1=CC=CC=C1 CUQCMXFWIMOWRP-UHFFFAOYSA-N 0.000 claims description 2
- LFKDJXLFVYVEFG-UHFFFAOYSA-N tert-butyl carbamate Chemical compound CC(C)(C)OC(N)=O LFKDJXLFVYVEFG-UHFFFAOYSA-N 0.000 claims description 2
- 229940123208 Biguanide Drugs 0.000 claims 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000000110 selective laser sintering Methods 0.000 abstract 2
- 238000004132 cross linking Methods 0.000 abstract 1
- DDYDBBBQYLFRJE-UHFFFAOYSA-N (diaminomethylideneamino)urea Chemical compound NC(=N)NNC(N)=O DDYDBBBQYLFRJE-UHFFFAOYSA-N 0.000 description 14
- 238000001723 curing Methods 0.000 description 9
- 238000000016 photochemical curing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007639 printing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VNSFGLSIVSOPEC-UHFFFAOYSA-N guanidine;urea Chemical compound NC(N)=N.NC(N)=O VNSFGLSIVSOPEC-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The application belongs to the technical field of new materials, and provides 3D printed self-repairing silicone rubber and a preparation method thereof, wherein the 3D printed self-repairing silicone rubber mainly comprises hydroxy-terminated polydimethylsiloxane, diisocyanate, guanidino compound, crosslinking group and solvent, and the preparation method of the 3D printed self-repairing silicone rubber comprises the following steps: sequentially dissolving hydroxyl-terminated polydimethylsiloxane, a catalyst, diisocyanate, a guanidyl compound and a cross-linking agent in a solvent according to certain parts by weight, stirring and reacting to obtain a prepolymer, pouring the prepolymer into a mold after the reaction is finished, and curing at room temperature, heating and curing to remove the solvent to obtain the 3D-printed self-repairing silicone rubber material. The silicone rubber disclosed by the application has high mechanical strength and good thermoplasticity, is suitable for various 3D printing processing modes such as fuse manufacturing (FFF), heating ink direct writing (DIW), selective Laser Sintering (SLS) and the like, is nontoxic and harmless, has a self-repairing function, and is applied to the fields of flexible sensors, biomedical and the like.
Description
Technical Field
The application belongs to the technical field of new materials, and relates to 3D printing self-repairing silicone rubber and a preparation method thereof.
Background
Polydimethylsiloxane (PDMS) is one of the most promising elastomers because of its good thermal stability, biocompatibility, corrosion resistance, flexibility, low cost, ease of use, chemical inertness, proliferation and breathability. Thus, it is useful in the fields of microfluidic systems, biomedical devices, electronic components, filtration and pervaporation membranes, sensors and coatings, and the like.
Currently, silicone rubbers that can be used for 3D printing have been reported. CN115637048A discloses a photo-curing 3D printing silicone rubber ink and a preparation method thereof, the photo-curing 3D printing silicone rubber ink of the application has the advantage of high precision molding, and the formula of the application is scientific, so that the photo-curing 3D printing silicone rubber ink has a relatively high photo-curing speed, can be cured within 5s at normal temperature, and has no obvious peculiar smell and shrinkage after curing. However, the mechanical strength of the photo-curing 3D printing silicone rubber product is not high and is only 0.6MPa, the printing method is single, the residual photoinitiator also has potential biotoxicity, and the photo-curing 3D printing silicone rubber product does not contain dynamic bonds and does not have self-repairing performance.
Based on the analysis, the self-repairing silicone rubber prepared by printing has high mechanical strength, no biological toxicity and self-repairing performance, and the preparation method thereof is urgently needed in industry.
Disclosure of Invention
In view of the above-mentioned shortcomings, the application aims to solve the problems that the existing 3D printing silicone rubber is single in printing means, low in mechanical strength and free of self-repairing performance, and provides 3D printing self-repairing silicone rubber and a preparation method thereof, wherein guanidine urea dynamic bonds are obtained by reacting guanidine groups with isocyanate, so that the novel thermal response type dynamic bonds are formed, a cross-linked silicone rubber material can flow by heating, and has heatable processability, and can be used for manufacturing a 3D printing processing mode of a fuse, and meanwhile, the dynamic bond reaction enhances interlayer binding force of a printed product, reduces mechanical slight anisotropy of the product, and enables the printed product to have self-repairing performance. The silicone rubber disclosed by the application has excellent mechanical properties, can be used for various 3D printing processing modes, has a self-repairing function, and is simple in preparation process and relatively low in cost.
In order to achieve the above purpose, the application adopts the following technical means:
the application discloses a 3D printed self-repairing silicon rubber, which comprises the following components:
25-33 parts of hydroxyl-terminated polydimethylsiloxane;
0.1-1 part of catalyst;
33-45 parts of diisocyanate;
4-23 parts of guanidino compound;
1-5 parts of cross-linking agent; and
20-100 parts of solvent.
Further, the hydroxyl-terminated polydimethylsiloxane is one or more of hydroxyl-terminated polydimethylsiloxanes with molecular weights of 500-30000.
Further, the catalyst is one or more of triethylamine, dibutyl tin dilaurate, N-methylmorpholine, dinonylnaphthalene disulfonic acid and triphenylphosphine.
Further, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
Further, the guanidyl compound is one or more of N- [ 1-amino-1-morpholin-4-ylmethyl-subunit ] -guanidine, (1E) -1- [ amino- (4-chloro, anilino) methylene ] -2-propyl-2-yl guanidine, phenyl biguanide, metformin, carbamic acid tert-butyl ester, 1-o-tolylbiguanide, phenformin and N-phenethyl biguanide.
Further, the cross-linking agent is one or more of hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and toluene diisocyanate trimer.
Further, the solvent is one or more of acetone, isopropanol, ethyl acetate, tetrahydrofuran, 1, 4-dioxane, dichloromethane, chloroform and toluene.
The application also discloses a preparation method of the 3D printing self-repairing silicone rubber, which comprises the following steps:
(1) Sequentially dissolving the raw materials in a solvent to obtain a reaction solution, and stirring and reacting for 3-9 hours at room temperature to obtain a prepolymer;
(2) Pouring the prepolymer into a mold, curing for a period of time at room temperature by using a solvent, then placing the prepolymer into an oven to remove the solvent and continuously curing, and obtaining a silicone rubber solid after curing is completed;
(3) And shearing and crushing the silicon rubber solid to obtain the 3D printed self-repairing silicon rubber.
Further, the raw materials in the step (1) are added in the following sequence: hydroxyl-terminated polydimethylsiloxane, catalyst, diisocyanate, guanidino compound and crosslinking agent.
Further, the room temperature curing and solvent removing time in the step (2) is 12-36 hours, the temperature in the oven is 80 ℃, and the time for removing the solvent and continuing to cure in the oven is 36-72 hours.
Further, the solvent vapor in the process of removing the solvent in the drying oven of the prepolymer in the step (2) is recovered by a solvent recovery machine.
The application also discloses the 3D printed self-repairing silicone rubber prepared by any one of the preparation methods.
The application has the beneficial effects that:
1) In the application, the guanidine compound in the raw material has a polyurea chain segment on the main chain of molecular weight, so that the mechanical strength of the material can be obviously improved, and the tensile strength can reach 14.5MPa.
2) In the application, the guanylurea in the 3D printing self-repairing silicone rubber containing the guanylurea dynamic bond is a thermal reversible chemical bond, can be broken at high temperature, and can be regenerated after the temperature is reduced, so that the prepared crosslinked silicone rubber has reworkability.
3) According to the application, the 3D printing self-repairing silicone rubber containing the guanidyl urea dynamic bond has self-repairing performance, and the 3D printing product can realize damage repair under the condition of no external repairing agent or catalyst.
4) In the application, the raw materials are easy to obtain, the synthesis process is simple and easy to control, the yield is high, and the method is nontoxic.
Drawings
FIG. 1 is a chemical structural formula of 3D printed self-repairing silicone rubber containing guanidyl urea dynamic bond prepared in example 1;
FIG. 2 is an infrared spectrum of 3D printed self-repairing silicone rubber containing guanidyl urea dynamic bond prepared in example 1;
FIG. 3 is a physical diagram of 3D printed self-repairing silicone rubber containing guanidyl urea dynamic bond prepared in example 1;
FIG. 4 is a shear crushed pictorial view of 3D printed self-repairing silicone rubber containing guanidyl urea dynamic bond prepared in example 1;
FIG. 5 is a thermogravimetric plot of 3D printed self-healing silicone rubber containing guanidyl urea dynamic bonds prepared in example 2;
FIG. 6 is a graph of applied strain before and after repair of damage to a 3D printed self-repairing silicone rubber tensile spline containing guanidyl urea dynamic bonds prepared in example 2;
FIG. 7 is a temperature-swing rheological profile of 3D printed self-healing silicone rubber containing guanidyl urea dynamic bonds prepared in example 2;
FIG. 8 is a 3D printed self-repairing silicone rubber printed tensile bar physical graph containing guanidyl urea dynamic bond prepared in example 3;
FIG. 9 is a graph of 3D printed self-repairing silicone rubber printed tensile spline stress strain containing guanidyl urea dynamic bonds prepared in example 3;
fig. 10 is an electron micrograph of a 3D printed self-healing silicone rubber fuse-fabricated extruded filament containing guanidyl urea dynamic bond prepared in example 3.
Detailed Description
The 3D printing equipment and the raw materials used in the embodiment of the application are all known products, and are obtained by purchasing commercial products through purchasing markets. The specific technical scheme of the application is described by combining the embodiment:
example 1
1. Preparation of a Silicone rubber prepolymer
(1) The hydroxyl-terminated polydimethylsiloxane (molecular weight 1000, 30 parts), catalyst dibutyltin dilaurate (0.5 parts) and isophorone diisocyanate (39 parts) were weighed in proportion and dissolved in the solvent 1, 4-dioxane (25 parts), and the reaction was stirred at room temperature for 2 hours.
(2) 1-o-tolylbiguanide (13.5 parts) and solvent 1, 4-dioxane (25 parts) were weighed in proportion and dissolved in the above reaction solution, and stirring was continued at room temperature for 2 hours.
(3) Finally, the crosslinking agent hexamethylene diisocyanate trimer (3 parts) and the solvent 1, 4-dioxane (25 parts) are weighed according to the proportion and dissolved in the reaction liquid, and stirring is continued for 2 hours at room temperature.
(4) Pouring the prepolymer obtained in the step (3) into a polytetrafluoroethylene mould, removing solvent at room temperature for curing for 24 hours, putting into an oven at 80 ℃ for removing solvent, and continuously curing for 48 hours, wherein solvent steam is recovered by a solvent recovery machine.
The chemical structures of the raw materials and the synthetic silicone rubber in the embodiment are shown in fig. 1, the infrared spectrum detection is carried out on the obtained silicone rubber, the detection structure is shown in fig. 2, and the physical diagram is shown in fig. 3. The particles obtained after shearing and pulverizing the silicone rubber solid are shown in fig. 4. As can be seen from fig. 2: the silicone rubber has chemical crosslinking structure, and has characteristic peak (2240-2280 cm) -1 ) And the components are completely reacted after disappearing.
Example 2
1. Preparation of a Silicone rubber prepolymer
(1) The hydroxyl-terminated polydimethylsiloxane (molecular weight 2000, 25 parts), the catalyst triethylamine (0.9 parts) and lysine diisocyanate (39 parts) were weighed in proportion and dissolved in the solvent tetrahydrofuran (20 parts), and the reaction was stirred at room temperature for 3 hours.
(2) N- [ 1-amino-1-morpholin-4-ylmethyl-subunit ] -guanidine (15 parts) and solvent tetrahydrofuran (20 parts) were weighed in proportion and dissolved in the above reaction solution, and stirring was continued at room temperature for 3 hours.
(3) Finally, the hexamethylene diisocyanate trimer (3 parts) as a crosslinking agent and tetrahydrofuran (20 parts) as a solvent were weighed in proportion and dissolved in the reaction solution, and stirring was continued at room temperature for 3 hours.
(4) Pouring the prepolymer obtained in the step (3) into a polytetrafluoroethylene mould, removing solvent at room temperature for curing for 12 hours, putting into an oven at 80 ℃ for removing solvent, and continuously curing for 36 hours, wherein solvent steam is recovered by a solvent recovery machine.
The silicone rubber obtained in example 2 was subjected to thermogravimetric analysis, the test results are shown in fig. 5, the thin neck of the silicone rubber spline molded in test example 2 was cut with a blade, then both end faces were bonded together, and the resultant was placed in an oven at 110 ℃ for 3 hours, and then subjected to mechanical test, and the test results are shown in fig. 6. As can be seen from fig. 5: the initial temperature of the weight loss of the silicone rubber elastomer is 211 ℃, and the weight loss between 211 ℃ and 303 ℃ is 10 percent, which shows that the silicone rubber synthesized in the example 2 has good heat stability; as can be seen from fig. 6: the guanylurea obtained by the reaction of guanidyl and isocyanate is a thermally responsive dynamic bond, so that the silicone rubber product has self-repairing property, and the damage of the product can realize 90% self-healing at 110 ℃. The resultant silicone rubber was subjected to a variable temperature rotational rheology test, the test results of which are shown in fig. 7, and the viscosity of the silicone rubber was reduced to zero at around 140 c, indicating that the temperature of the silicone rubber print window synthesized in example 2 was about 140 c.
Example 3
The guanidino urea dynamic bond-containing silicone rubber particles prepared in example 1 were used for fuse making (FFF) 3D printing, printing parameters: build chamber (plateau) temperature 80 ℃, screw temperature 135 ℃, droplet size ratio 1.315, continuous extrusion feed rate 20, continuous extrusion feed rate 65, internal and external correction factor value 1.0.
The 3D printed tensile bars are shown in fig. 8, the stress-strain curves of the 3D printed tensile bars are shown in fig. 9, and the electron microscope image of the 3D printed fuse-fabricated silicone rubber extruded filaments is shown in fig. 10. The tensile strength of the 3D printing silicone rubber containing the guanidyl urea dynamic bond can reach 1.5MPa, and compared with the strength of the 3D printing silicone rubber material in the prior art which is only 0.6MPa, the tensile strength of the material is obviously improved.
In summary, the guanidyl urea dynamic bond is obtained by reacting guanidyl and isocyanate, is a novel thermal response type dynamic bond, can enable a crosslinked silicone rubber material to flow under heating, has hot workability, adopts a 3D printing processing mode for manufacturing fuses, enhances interlayer bonding force of printed products, reduces mechanical strength anisotropy of the printed products, enables the printed products to have a self-repairing function, can repair product damage at 110 ℃, improves mechanical strength of the material, is excellent in mechanical property, is suitable for 3D printing for manufacturing fuses, has the self-repairing function, and is simple in preparation process and relatively low in cost. Therefore, the application effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. A 3D printed self-healing silicone rubber comprising:
25-33 parts of hydroxyl-terminated polydimethylsiloxane;
0.1-1 part of catalyst;
33-45 parts of diisocyanate;
4-23 parts of guanidino compound;
1-5 parts of cross-linking agent; and
20-100 parts of solvent.
2. The self-healing silicone rubber of claim 1, wherein:
the hydroxyl-terminated polydimethylsiloxane is one or more of hydroxyl-terminated polydimethylsiloxanes with molecular weights of 500-30000.
3. The self-healing silicone rubber of claim 1, wherein:
the catalyst is one or more of triethylamine, dibutyl tin dilaurate, N-methylmorpholine, dinonyl naphthalene disulfonic acid and triphenylphosphine.
4. The self-healing silicone rubber of claim 1, wherein:
the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
5. The self-healing silicone rubber of claim 1, wherein:
the guanidyl compound is one or more of N- [ 1-amino-1-morpholin-4-ylmethyl-subunit ] -guanidine, (1E) -1- [ amino- (4-chlorine, anilino) methylene ] -2-propyl-2-yl guanidine, phenyl biguanide, metformin, carbamic acid tert-butyl ester, 1-o-toluene biguanide, phenformin and N-phenethyl biguanide.
6. The self-healing silicone rubber of claim 1, wherein:
the cross-linking agent is one or more of hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and toluene diisocyanate trimer.
7. The self-healing silicone rubber of claim 1, wherein:
the solvent is one or more of acetone, isopropanol, ethyl acetate, tetrahydrofuran, 1, 4-dioxane, dichloromethane, chloroform or toluene.
8. A method of preparing a 3D printed self-healing silicone rubber according to any one of claims 1 to 7, comprising:
(1) Sequentially dissolving the raw materials in a solvent to obtain a reaction solution, and stirring and reacting for 3-9 hours at room temperature to obtain a prepolymer;
(2) Pouring the prepolymer into a mold, curing for a period of time at room temperature by using a solvent, then placing the prepolymer into an oven to remove the solvent and continuously curing, and obtaining a silicone rubber solid after curing is completed;
(3) And shearing and crushing the silicon rubber solid to obtain the 3D printed self-repairing silicon rubber.
9. The method of manufacturing according to claim 8, wherein:
the adding sequence of the raw materials in the step (1) is as follows: hydroxyl-terminated polydimethylsiloxane, catalyst, diisocyanate, guanidino compound and crosslinking agent;
and (3) the room-temperature curing and solvent removing time is 12-36 hours, the temperature in the oven is 80 ℃, and the time for removing the solvent and continuing to cure in the oven is 36-72 hours.
10. A 3D printed self-healing silicone rubber made according to the method of making of claim 8 or 9.
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