CN114573986A - 3D printing part capable of being completely degraded and recycled, and preparation method and application thereof - Google Patents
3D printing part capable of being completely degraded and recycled, and preparation method and application thereof Download PDFInfo
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- CN114573986A CN114573986A CN202011384127.XA CN202011384127A CN114573986A CN 114573986 A CN114573986 A CN 114573986A CN 202011384127 A CN202011384127 A CN 202011384127A CN 114573986 A CN114573986 A CN 114573986A
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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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Abstract
The invention discloses a 3D printing part capable of being completely degraded and recycled, and a preparation method and application thereof. The product is prepared by the following composition system: (A) a mixed dispersion of a siloxane hydrolysate and an alkali solution; (B) a low surface energy polymer solution; and (C) an inorganic filler. The 3D printing part provided by the invention can be completely degraded into monomers in water or a water-containing solvent under the heating condition, so that the complete degradation and recovery of the part are realized, the recovery method is simple and convenient, and the recovery efficiency is high; but reuse carries out 3D printing shaping many times, and material utilization is high.
Description
Technical Field
The invention belongs to the field of 3D printing, and particularly relates to a 3D printing part capable of being completely degraded and recycled, and a preparation method and application thereof.
Background
3D printing has attracted considerable attention as a novel molding technique in many fields such as architecture, aerospace, biomedical, and smart devices. Compare in traditional processing mode, 3D prints and can directly the shaping complex construction, need not mould and loaded down with trivial details process flow. The polymer material is the most common material in 3D printing, and is suitable for various printing modes such as direct writing printing, melt extrusion molding, digital light processing printing, selective laser sintering and the like. However, thermoplastic or thermosetting polymer materials for 3D printing are difficult to degrade in nature due to their stable chemical structures, and the use of such materials in large quantities causes serious environmental pollution along with the rapid development of 3D printing.
In order to solve the problems, at present, biodegradable materials such as polylactic acid are mostly adopted as 3D printing raw materials, but the polylactic acid material has poor mechanical property and heat resistance and is difficult to meet increasingly harsh use environments, and meanwhile, the polylactic acid material also has the problems that the degradation period is long and the polylactic acid material cannot be recycled, so that the development of a completely degradable and recyclable 3D printing material is very necessary.
Disclosure of Invention
The present invention provides a composition system for preparing a 3D printed article comprising:
(A) a mixed dispersion of a siloxane hydrolysate and an alkali solution;
(B) a low surface energy polymer solution; and
(C) an inorganic filler.
The invention also provides a 3D printing part prepared from the composition system.
Preferably, the 3D printed article is fully degradable and recyclable.
The invention also provides a preparation method of the 3D printing part, which comprises the following steps:
mixing (A) a mixed dispersion of siloxane hydrolysate and an alkali solution, (B) a low surface energy polymer solution and (C) an inorganic filler to prepare a composition system; and 3D printing, drying and heat treatment are carried out on the composition system to obtain the 3D printed product.
According to an embodiment of the invention, the preparation method comprises the steps of:
1) mixing the siloxane hydrolysate with an alkali solution to prepare a mixed dispersion of the siloxane hydrolysate and the alkali solution (A);
preferably, the siloxane hydrolysate is prepared from siloxane monomers under the condition of catalytic heating;
2) dissolving a low surface energy polymer in a solvent a to obtain (B) a low surface energy polymer solution;
3) mixing the siloxane hydrolysate and alkali solution mixed dispersion liquid (A), the low surface energy polymer solution (B) and the inorganic filler (C) to prepare a composition system;
4) 3D printing is carried out on the composition system to obtain an initial part;
5) and drying and thermally treating the initial workpiece to obtain the 3D printing workpiece.
The invention also provides a 3D printing part prepared by the method.
The invention also provides a recovery method of the 3D printing part, which comprises the following steps: and (3) placing the 3D printing part in water or a water-containing solvent for a period of time to obtain a sol dispersion liquid.
Wherein the aqueous solvent may be selected from a mixed solvent of water and an organic solvent.
The invention also provides a recycling method of the 3D printing part, which comprises the following steps: 3D printing the recovered sol dispersion liquid again, and then drying and carrying out heat treatment to obtain a reshaped 3D printed part;
the 3D printing, drying and heat treatment are the same as the operations in the preparation method of the 3D printed product.
The invention also provides a reshaped 3D printed article prepared by the recycling method.
The invention also provides the application of the combined object system in the preparation of 3D printing parts which can be completely degraded and/or recycled.
The invention has the beneficial effects that:
1. the preparation method of the 3D printing part provided by the invention is simple, and the 3D printing part can be prepared by blending the solution under mild conditions and performing 3D printing, drying and heat treatment (such as a sintering step) on the blended solution.
2. The 3D printing part provided by the invention can be completely degraded into monomers in water or a water-containing solvent (preferably under a heating condition), so that the complete degradation and recovery of the part are realized, the recovery method is simple and convenient, and the recovery efficiency is high.
3. The sol dispersion liquid recovered by the method can be recycled, and is subjected to 3D printing and forming for many times, so that the material utilization rate is high.
4. The 3D printing part provided by the invention has higher mechanical property, and the mechanical property of the 3D printing part which is formed again after being completely degraded and recovered is equal to that of the initial part.
5. The 3D printing fully degradable and recyclable part prepared by the invention has the functions of recycling, heat resistance, pollution resistance and the like, and has wide application prospect.
Drawings
Fig. 1 is a photograph of the process of preparing a fully degradable recycled 3D printed article in example 1.
Fig. 2 is a photograph of the fully degradable recycled 3D printed article prepared in example 1 after recycling and dissolution.
Fig. 3 is a mass spectrum of a recovery solution of a fully degradable recovered 3D printed article prepared in example 1.
Fig. 4 is a graph of the hardness of the fully degradable recycled 3D printed article prepared in example 1 after multiple recycles.
Fig. 5 is a graph of the three-point bending performance of the fully degradable recycled 3D printed article and the one-shot recycled article prepared in example 1.
Fig. 6 shows the thermal performance of the fully degradable recycled 3D printed article prepared in example 1.
FIG. 7 is a graph showing the stain resistance of the fully degradable recycled article prepared in example 1.
Detailed Description
[ composition System for preparing 3D-printed articles ]
As mentioned above, the present invention proposes a composition system for the preparation of 3D printed articles comprising:
(A) a mixed dispersion of a siloxane hydrolysate and an alkali solution;
(B) a low surface energy polymer solution;
(C) an inorganic filler.
According to an embodiment of the present invention, the composition system has a mass ratio of (A) the mixed dispersion of the siloxane hydrolyzate and the alkali solution, (B) the low surface energy polymer solution and (C) the inorganic filler of (100) -.
[ component (A) in the composition System ]
In the composition system, the mixed dispersion liquid of the siloxane hydrolysate and the alkali solution (A) comprises the siloxane hydrolysate and the alkali solution. The siloxane hydrolysate is prepared from silane coupling agent monomers under the condition of catalytic heating.
Wherein the preparation raw material of the siloxane hydrolysate comprises siloxane monomers, a catalyst and a solvent c. Wherein the siloxane monomer may be selected from at least one of siloxanes having hydrophobic end groups, such as methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like; preferably at least one of propyltrimethoxysilane, dodecyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, ethyltriethoxysilane, and gamma-mercaptopropyltrimethoxysilane.
Wherein the catalyst is selected from hydrochloric acid or at least one of sodium hydroxide and potassium hydroxide, such as hydrochloric acid, sodium hydroxide or potassium hydroxide, and is exemplified by hydrochloric acid.
Wherein, the preparation raw materials of the alkali solution comprise organic alkali and a solvent c. For example, the organic base is selected from at least one of dimethylamine, trimethylamine, ethylamine, triethylamine, benzylamine, aniline, p-toluidine, p-chloroaniline, p-nitroaniline, diphenylamine, pyridine, triethanolamine and urea; for example, at least one of dimethylamine, trimethylamine, ethylamine, triethylamine and aniline; exemplified are trimethylamine, triethylamine, triethanolamine, diphenylamine and/or aniline.
Wherein the solvent c is at least one selected from ethanol, acetone, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, methanol, isopropanol, toluene, cyclohexane, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; for example, at least one selected from ethanol, methanol and isopropanol, and exemplified by ethanol.
Wherein, in the siloxane hydrolysate, the mass ratio of the catalyst, the siloxane monomer and the solvent c is 1 (50-1000): 100-.
Wherein, in the alkali solution, the mass ratio of the organic alkali to the solvent c is 1 (50-5000), such as 1 (100-2000), and the examples are 1:100, 1:500, 1:600 and 1: 800.
Wherein in the mixed dispersion liquid of the siloxane hydrolysate and the alkali solution (A), the mass ratio of siloxane monomer, the catalyst, the organic base and the solvent c is (5-10000):1 (0.5-100): 100-.
[ component (B) in the composition System ]
The low surface energy polymer solution comprises a low surface energy polymer and a solvent a.
Wherein the low surface energy polymer is selected from at least one of fluorocarbon resin, organic silicon resin and fluorine-silicon resin. For example, the fluorocarbon resin includes a low surface energy polymer containing a fluorine atom in a polymer chain, preferably at least one of polytetrafluoroethylene resin (PTFE), polyvinylidene fluoride resin (PVDF), polychlorotrifluoroethylene resin (FEVE), polyvinyl fluoride resin (PVF), and the like; exemplary is polytetrafluoroethylene resin (PTFE). For example, the silicone resin includes polysiloxane having a Si — O skeleton in its main chain, preferably at least one of polymers such as methyl silicone resin, phenyl vinyl silicone resin, phenyl epoxy silicone resin, borosilicate resin, and poly-n-hexyltriphenylethynyl silane resin, and is exemplified by polymethyl silicone resin or phenyl vinyl silicone resin. For example, the fluorosilicone resin includes a low surface energy material having advantages and superior properties of each of a fluorocarbon resin and a silicone resin, and is preferably at least one of polytrifluoropropylmethylsiloxane, polymethylnonafluorohexylsiloxane, polytridecylfluorooctylmethylsiloxane, and polymethylheptadecafluorodecylsiloxane, and is exemplified by polytrifluoropropylmethylsiloxane.
Wherein the weight average molecular weight of the fluorocarbon resin is 5000-.
Wherein the weight average molecular weight of the silicone resin is 1000-.
Wherein the weight average molecular weight of the fluorosilicone resin is 3000-300 ten thousand, for example, 5000-150 ten thousand, or, for example, 1-75 ten thousand, and an exemplary value is 1 ten thousand.
Wherein the solvent a is selected from ketone solvents and/or ester solvents, such as at least one selected from acetone, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate and the like; illustrative are ethyl acetate, methyl butanone or methyl isobutyl ketone.
The concentration of the low surface energy polymer solution is 0.1 to 100mg/mL, such as 5 to 25mg/mL, exemplary 10mg/mL, 12.5mg/mL, 15mg/mL, 20mg/mL, 25 mg/mL.
[ component (C) in the composition System ]
The inorganic filler is selected from at least one of silicon dioxide, zirconium dioxide, ferroferric oxide, titanium dioxide, montmorillonite, boron nitride, graphene, molybdenum disulfide, graphene oxide, carbon nano tubes, MXene nano sheets, liquid metal and metal nano particles; wherein the metal nanoparticles may be selected from at least one of gold nanoparticles, silver nanoparticles, and copper nanoparticles.
Preferably, the inorganic filler is selected from at least one of silicon dioxide, zirconium dioxide, carbon nanotubes, montmorillonite, graphene oxide, titanium dioxide, and boron nitride.
[3D printing product ]
The invention provides 3D printed articles prepared from the above composition system. Preferably, the 3D printed article is capable of complete degradation recycling.
[ preparation method of 3D printed article ]
The invention also provides a preparation method of the 3D printing part, which comprises the following steps:
mixing (A) a mixed dispersion of siloxane hydrolysate and an alkali solution, (B) a low surface energy polymer solution and (C) an inorganic filler to prepare a composition system; and 3D printing, drying and heat treatment are carried out on the composition system to obtain the 3D printing part.
According to an embodiment of the invention, the preparation method comprises the following steps:
1) mixing the siloxane hydrolysate with an alkali solution to prepare a mixed dispersion of the siloxane hydrolysate and the alkali solution (A);
preferably, the siloxane hydrolysate is prepared from siloxane monomers under the condition of catalytic heating;
2) dissolving a low surface energy polymer in a solvent a to obtain (B) a low surface energy polymer solution;
3) mixing the siloxane hydrolysate and alkali solution mixed dispersion liquid (A), the low surface energy polymer solution (B) and the inorganic filler (C) to prepare a composition system;
4) 3D printing is carried out on the composition system to obtain an initial printing part;
5) and drying and thermally treating the initial 3D printed part to obtain the 3D printed part.
In step 1), the mass ratio of the siloxane hydrolysate to the alkali solution is (5-10000):1, for example, (10-1000):1, and further for example, (10-500):1, exemplary 30:1, 50:1, 100:1, 300: 1.
Wherein, in the alkali solution, the mass ratio of the organic alkali to the solvent c is 1 (10-5000), such as 1 (10-1000), and the examples are 1:100, 1:400, 1:500, 1:600 and 1: 800.
In the step 1), the preparation raw materials of the siloxane hydrolysate comprise siloxane monomers, a catalyst and a solvent c. Wherein, the siloxane monomer, the catalyst, the solvent c and the mixture ratio thereof have the meanings as described above.
In the step 1), the mass ratio of the catalyst to the solvent c is 1 (100-10000), such as 1 (150-1000), and also such as 1 (300-600), and exemplary is 1:133, 1:300, 1:400, 1:500, 1:600, 1:700, and 3: 700.
In step 1), the mass ratio of the catalyst to the siloxane monomer is 1 (50-1000), such as 1 (100-800), and exemplary is 1:300, 6:2500, 1:150, 1:400, and 3: 400.
In step 1), the catalytic heating conditions include: the temperature is 50-100 deg.C, such as 70-90 deg.C, and exemplary temperatures are 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C. Further, the reaction time of the catalytic heating is 1 to 10h, such as 2 to 8h, exemplary 5h, 7h, 8h, 10 h.
In step 1), the catalytic heating is performed under stirring conditions, such as a stirring speed of 200-.
The dissolving in the step 2) is stirring dissolving. For example, the stirring speed is 200-5000rpm, such as 500-3000rpm, and exemplary speeds are 2000rpm and 3000 rpm. Further, the stirring time is 1 to 10 days, such as 3 to 7 days, illustratively 3 days, 4 days, 6 days, 7 days.
In the step 3), the mass ratio of the mixed dispersion of the siloxane hydrolysis liquid and the alkali solution (A) to the inorganic filler (C) is (100-1500): (0.1-100), such as (300-1000): 5-20), and further such as (100-200):1, illustratively 10:1, 25:1, 100:1, 150:1, 200: 1.
In the step 4), the 3D printing is direct ink writing 3D printing.
In step 5), the drying temperature is 80-200 deg.C, such as 160 deg.C, for example, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 130 deg.C, 150 deg.C.
In step 5), the heat treatment may be a sintering treatment, such as under protection of an inert atmosphere, for example, provided by at least one of nitrogen and argon, etc., preferably nitrogen.
In step 5), the temperature of the heat treatment is 200-. Further, the time of the heat treatment is 0.5 to 24 hours, such as 1 to 6 hours, exemplary 1 hour, 3 hours, 4 hours, 5 hours, 10 hours.
In the present invention, the (a) mixed dispersion of the siloxane hydrolyzate and the alkali solution, (B) the low surface energy polymer solution, (C) the inorganic filler, the siloxane hydrolyzate, the alkali solution, the organic base, the catalyst, the low surface energy polymer, the solvent a, the solvent B, and the solvent C have the meanings as described above.
[ method for recovering 3D-printed article ]
The invention also provides a recovery method of the 3D printing part, which comprises the following steps: and (3) placing the 3D printing part in water or a water-containing solvent for a period of time to obtain a sol dispersion liquid.
Wherein the aqueous solvent may be selected from a mixed solvent of water and an organic solvent. Preferably, the organic solvent is a water-miscible organic solvent, such as ethanol.
Preferably, the 3D printed article is placed in water or an aqueous solvent under heating for a period of time to obtain a sol dispersion. For example, the temperature of the heating is 50 to 100 ℃ (e.g., 80 ℃); the time for standing in water or an aqueous solvent is not limited, and a transparent sol dispersion can be obtained.
Wherein the 3D printed article is fully degradable in water or aqueous solvent; preferably, the sol dispersion contains monomers formed by degradation of the 3D printed article.
[ Recycling method of 3D printed article ]
The invention also provides a recycling method of the 3D printing part, which comprises the following steps: 3D printing the recovered sol dispersion liquid again, and then drying and carrying out heat treatment to obtain a reshaped 3D printed part;
the 3D printing, drying and heat treatment are the same as the operations in the preparation method of the 3D printed product.
[ reshaped 3D-printed article ]
The invention also provides a reshaped 3D printed article prepared by the recycling method.
[ application ]
The invention also provides the application of the combined object system in the preparation of 3D printing parts which can be completely degraded and/or recycled.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
1) Under the catalytic action of hydrochloric acid, dissolving propyl trimethoxy silane in ethanol, heating the mixture at 80 ℃, stirring at 2000rpm for 10h to prepare a hydrolysis dispersion liquid of propyl trimethoxy silane, namely a hydrolysis liquid a; wherein the mass ratio of the hydrochloric acid to the propyl trimethoxy silane to the ethanol is 1:300: 500;
2) dissolving organic alkali triethanolamine in ethanol at a weight ratio of triethanolamine to ethanol of 1:100 to obtain ethanol solution of triethanolamine, i.e. solution b;
3) dissolving 2.5g of low surface energy polymer polytetrafluoroethylene resin with the weight average molecular weight of 1 ten thousand in 200mL of ethyl acetate, and magnetically stirring for 3 days at normal temperature at the rotating speed of 1000rpm to obtain a polytetrafluoroethylene solution, namely solution c;
4) blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 300:1 to obtain a mixed dispersion liquid, namely a dispersion liquid d;
5) blending the dispersion liquid d prepared in the step 4), the solution c prepared in the step 3) and silicon dioxide in a mass ratio of 500:1:50 to prepare a mixed dispersion liquid e;
6) putting the dispersion liquid e obtained in the step 5) into an injector of a direct writing printer, setting a program, and then printing a designed workpiece;
7) drying the product obtained in the step 6) at 80 ℃ for 24h, and then sintering the product at 300 ℃ for 3h in a nitrogen atmosphere to obtain the original 3D printing product.
A photograph of the process for preparing a fully degradable and recyclable 3D printed article in this example is shown in fig. 1.
Example 2
1) Under the catalytic action of hydrochloric acid, dissolving dodecyl triethoxysilane in ethanol, heating the mixture at 70 deg.C, stirring at 1000rpm for 8h to obtain hydrolysis dispersion of dodecyl triethoxysilane, i.e. hydrolysate a; wherein the mass ratio of the hydrochloric acid to the dodecyl triethoxy silane to the ethanol is 1:150: 500;
2) dissolving organic base triethylamine in ethanol, wherein the mass ratio of the triethylamine to the ethanol is 1:500, and preparing an ethanol solution of the triethylamine, namely solution b;
3) dissolving 2.5g of low surface energy polymer methyl silicone resin with the weight average molecular weight of 1 ten thousand in 200mL of acetone, and magnetically stirring for 5 days at normal temperature at the rotating speed of 3000rpm to obtain a methyl silicone resin solution, namely solution c;
3) dissolving 2.5g of low surface energy polymer polytetrafluoroethylene resin with the weight average molecular weight of 1 ten thousand in 200mL of ethyl acetate, and magnetically stirring for 3 days at normal temperature at the rotating speed of 1000rpm to obtain a polytetrafluoroethylene solution, namely solution c;
4) blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 300:1 to obtain a mixed dispersion liquid, namely a dispersion liquid d;
5) blending the dispersion liquid d prepared in the step 4), the solution c prepared in the step 3) and silicon dioxide according to the mass ratio of 500:1:50 to prepare a mixed dispersion liquid e;
6) putting the dispersion liquid e obtained in the step 5) into an injector of a direct writing printer, setting a program, and then printing a designed workpiece;
7) drying the product obtained in the step 6) at 80 ℃ for 24h, and then sintering the product at 300 ℃ for 3h in a nitrogen atmosphere to obtain the final product.
Example 3
1) Under the catalytic action of hydrochloric acid, dissolving propyl triethoxysilane in ethanol, heating the mixture at 60 deg.C, stirring at 800rpm for 7h to obtain hydrolysate of propyl triethoxysilane, i.e. hydrolysate a; wherein the mass ratio of the hydrochloric acid to the propyl triethoxysilane to the ethanol is 3:400: 700;
2) dissolving organic base triethylamine in ethanol, wherein the mass ratio of the triethylamine to the ethanol is 1:600, and preparing an ethanol solution of the triethylamine, namely solution b;
3) dissolving 5g of low surface energy polymer phenyl vinyl silicone resin with the weight average molecular weight of 1 ten thousand in 500mL of methyl butanone, and magnetically stirring at normal temperature for 6 days at the rotating speed of 2000rpm to obtain phenyl vinyl silicone resin solution, namely solution c;
4) blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 300:1 to obtain a mixed dispersion liquid, namely a dispersion liquid d;
5) blending the dispersion liquid d prepared in the step 4), the solution c prepared in the step 3) and graphene according to a mass ratio of 500:1:5 to prepare a mixed dispersion liquid e;
6) placing the dispersion liquid e obtained in the step 5) into an injector of a direct writing printer, setting a program, and then printing a designed workpiece;
7) drying the product obtained in the step 6) at 80 ℃ for 24h, and then sintering the product at 300 ℃ for 3h in a nitrogen atmosphere to obtain the final product.
Example 4
1) Under the catalytic action of hydrochloric acid, dissolving phenyltriethoxysilane in ethanol, heating the mixture at 80 deg.C, stirring at 1000rpm for 7h to obtain hydrolysate of phenyltriethoxysilane, i.e. hydrolysate a; wherein the mass ratio of the hydrochloric acid to the phenyltriethoxysilane to the ethanol is 1:400: 900;
2) dissolving organic alkali diphenylamine in ethanol, wherein the mass ratio of diphenylamine to ethanol is 1:600, and preparing an ethanol solution of diphenylamine, namely solution b;
3) dissolving 10g of low surface energy polymer poly (trifluoropropylmethylsiloxane) with the weight average molecular weight of 1 ten thousand in 500mL of methyl acetate, and magnetically stirring for 8 days at normal temperature at the rotating speed of 2000rpm to obtain poly (trifluoropropylmethylsiloxane) solution, namely solution c;
4) blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 300:1 to obtain a mixed dispersion liquid, namely a dispersion liquid d;
5) blending the dispersion liquid d prepared in the step 4) and the solution c prepared in the step 3) with montmorillonite according to the mass ratio of 500:1:20 to prepare a mixed dispersion liquid e;
6) placing the dispersion liquid e obtained in the step 5) into an injector of a direct writing printer, setting a program, and then printing a designed workpiece;
7) drying the product obtained in the step 6) at 70 ℃ for 24h, and then sintering the product at 300 ℃ for 3h in a nitrogen atmosphere to obtain the final product.
Example 5
1) Under the catalytic action of hydrochloric acid, dissolving ethyl triethoxysilane in ethanol, heating the mixture at 90 deg.C, stirring at 1000rpm for 8h to obtain hydrolysate a; wherein the mass ratio of the hydrochloric acid to the ethyl triethoxysilane to the ethanol is 1:150: 600;
2) dissolving organic alkali aniline in ethanol, wherein the mass ratio of aniline to ethanol is 1:800, and preparing ethanol dispersion liquid of aniline, namely solution b;
3) dissolving 25g of low surface energy polymer polytetrafluoroethylene resin with the weight average molecular weight of 1 ten thousand in 1000mL of propyl acetate, and magnetically stirring for 5 days at normal temperature at the rotating speed of 2000rpm to obtain polytetrafluoroethylene solution, namely solution c;
4) blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 300:1 to obtain a mixed dispersion liquid, namely a dispersion liquid d;
5) blending the dispersion liquid d prepared in the step 4), the solution c prepared in the step 3) and liquid metal in a mass ratio of 500:1:20 to prepare a mixed dispersion liquid e;
6) placing the dispersion liquid e obtained in the step 5) into an injector of a direct writing printer, setting a program, and then printing a designed workpiece;
7) and (3) drying the product obtained in the step 6) at 80 ℃ for 24h, and then sintering the product at 300 ℃ for 3h in a nitrogen atmosphere to obtain the final product.
Example 6
1) Dissolving gamma-mercaptopropyl trimethoxysilane in ethanol under the catalysis of hydrochloric acid, heating the mixture at 90 ℃, stirring at 2000rpm for 8 hours, and preparing hydrolysate of the gamma-mercaptopropyl trimethoxysilane, namely hydrolysate a; wherein the mass ratio of the hydrochloric acid to the gamma-mercaptopropyltrimethoxysilane to the ethanol is 6:2500: 3000;
2) dissolving organic alkali trimethylamine in ethanol, wherein the mass ratio of the trimethylamine to the ethanol is 1:800, and preparing an ethanol solution of the trimethylamine, namely solution b;
3) dissolving 15g of low surface energy polymer phenyl epoxy silicone resin with the weight average molecular weight of 1 ten thousand in 1000mL of methyl isobutyl ketone, and magnetically stirring at normal temperature for 10 days at the rotating speed of 2000rpm to obtain phenyl epoxy silicone resin solution, namely solution c;
4) blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 300:1 to obtain a mixed dispersion liquid, namely a dispersion liquid d;
5) blending the dispersion liquid d prepared in the step 4), the solution c prepared in the step 3) and zirconium dioxide according to the mass ratio of 500:1:20 to prepare a mixed dispersion liquid e;
6) putting the dispersion liquid e obtained in the step 5) into an injector of a direct writing printer, setting a program, and then printing a designed workpiece;
7) drying the product obtained in the step 6) at 80 ℃ for 24h, and then sintering the product at 300 ℃ for 5h in a nitrogen atmosphere to obtain the final product.
Example 7
The 3D printed article prepared in example 1 was placed in water at 80 ℃ for a period of time to give a clear and transparent solution (as shown in fig. 2).
The molecular weight of the recovered solution was determined using an Autoflex type III time-of-flight mass spectrometer (MALDI-TOF-MS), as shown in FIG. 3, and the molecular weight measured after recovery was concentrated around 400, indicating that the 3D-printed article had been completely degraded to a level comparable to the molecular weight of hydrolyzed propyltrimethoxysilane (molecular weight at about 250-300), i.e., completely degraded.
3D printing, drying and sintering the recovered clear and transparent solution again according to the conditions of the embodiment 1 to obtain a re-molded 3D printing part; dissolving the reshaped 3D printing part in water at 80 ℃ to obtain a clear and transparent solution; according to the above-mentioned process, the second, third, fourth and fifth recoveries and utilizations are carried out. The hardness of the original 3D printed part and the parts recovered many times is measured by a shore durometer, and the test result is shown in fig. 4. It can be seen that the hardness of the 3D printed product is almost unchanged before and after recycling, and the Shore hardness value is near 90.
Through three-point bending mechanical property test, the mechanical properties of the original 3D printed part and the 3D printed part after being recycled once are superior to those of organic glass, and the mechanical properties of the parts before and after being recycled are not changed greatly (as shown in figure 5).
Through thermogravimetric analysis (a TA Q600 thermogravimetric analyzer, temperature rising from room temperature to 1200 ℃, temperature rising speed 10 ℃/min, nitrogen atmosphere), the original 3D printed product prepared by the embodiment has excellent heat resistance, and the thermal decomposition temperature is greater than 400 ℃, as shown in fig. 6.
The kerosene oil was dropped on the surface of the sample, and the oil drops slipped off from the sample without leaving any trace, showing good antifouling properties of the sample, as shown in fig. 7.
Example 8
Using the same procedure of example 7, the articles of examples 2-6 were also able to give clear and transparent solutions in water which were also able to be reused to produce reshaped 3D printed articles having properties similar to those of example 7.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A composition system for making a 3D printed article, the composition system comprising:
(A) a mixed dispersion of a siloxane hydrolysate and an alkali solution;
(B) a low surface energy polymer solution; and
(C) an inorganic filler.
2. The composition system as claimed in claim 1, wherein the mass ratio of the (A) mixed dispersion of the siloxane hydrolyzate and the alkali solution, the (B) low surface energy polymer solution and the (C) inorganic filler is (100-1500):1 (0.1-100).
3. The composition system according to claim 1 or 2, wherein the mixed dispersion of (a) the siloxane hydrolysate and the alkali solution comprises the siloxane hydrolysate and the alkali solution.
Preferably, the siloxane hydrolysate is prepared from silane coupling agent monomers under the catalytic heating condition.
Preferably, the raw materials for preparing the siloxane hydrolysate comprise siloxane monomers, a catalyst and a solvent c.
Preferably, the siloxane monomer is selected from siloxanes having hydrophobic end groups, such as at least one of methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like.
Preferably, the preparation raw material of the alkali solution comprises an organic base and a solvent c. Preferably, the organic base is selected from at least one of dimethylamine, trimethylamine, ethylamine, triethylamine, benzylamine, aniline, p-toluidine, p-chloroaniline, p-nitroaniline, diphenylamine, pyridine, triethanolamine and urea.
Preferably, in the mixed dispersion liquid of the siloxane hydrolysate and the alkali solution (A), the mass ratio of the siloxane monomer, the catalyst, the organic base and the solvent c is (5-10000):1, (0.5-100): 100-10000).
4. The composition system according to any of claims 1 to 3, wherein the low surface energy polymer solution comprises a low surface energy polymer and a solvent a.
Preferably, the low surface energy polymer is selected from at least one of fluorocarbon resin, silicone resin, and fluorosilicone resin.
Preferably, the inorganic filler is selected from at least one of silicon dioxide, zirconium dioxide, ferroferric oxide, titanium dioxide, montmorillonite, boron nitride, graphene, molybdenum disulfide, graphene oxide, carbon nanotubes, MXene nanosheets, liquid metal and metal nanoparticles; preferably, the metal nanoparticles may be selected from at least one of gold nanoparticles, silver nanoparticles, and copper nanoparticles.
5. A 3D printed article, wherein the 3D printed article is prepared from the composition system of any of claims 1-4.
Preferably, the 3D printed article is fully degradable and recyclable.
6. The method of preparing a 3D printed article according to claim 5, comprising the steps of:
mixing (A) a mixed dispersion of siloxane hydrolysate and an alkali solution, (B) a low surface energy polymer solution and (C) an inorganic filler to prepare a composition system; and 3D printing, drying and heat treatment are carried out on the composition system to obtain the 3D printing part.
7. The method of claim 6, comprising the steps of:
1) mixing the siloxane hydrolysate with an alkali solution to prepare a mixed dispersion of the siloxane hydrolysate and the alkali solution (A);
preferably, the siloxane hydrolysate is prepared from siloxane monomers under the condition of catalytic heating;
2) dissolving a low surface energy polymer in a solvent a to obtain (B) a low surface energy polymer solution;
3) mixing the siloxane hydrolysate and alkali solution mixed dispersion liquid (A), the low surface energy polymer solution (B) and the inorganic filler (C) to prepare a composition system;
4) 3D printing is carried out on the composition system to obtain an initial part;
5) and drying and thermally treating the initial workpiece to obtain the 3D printing workpiece.
8. The recycling method of the 3D printed article as recited in claim 5, wherein the recycling method comprises the steps of: and (3) placing the 3D printing part in water or a water-containing solvent for a period of time to obtain a sol dispersion liquid.
Preferably, the aqueous solvent is selected from a mixed solvent of water and an organic solvent.
9. The recycling method of 3D printed articles of claim 5, wherein the recycling method comprises the steps of: 3D printing the sol dispersion recovered from claim 8 again, and then drying and heat treating to obtain a reshaped 3D printed part;
preferably, the 3D printing, drying and heat treating are the same as in the method of making the 3D printed article of claim 7.
10. Use of a composite object according to any one of claims 1 to 4 for the preparation of a fully degradable and/or recyclable 3D printed article.
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