SiZrOC resin capable of realizing photocuring 3D printing as well as preparation method and application of SiZrOC resin

Abstract

The invention discloses SiZrOC resin capable of realizing photocuring 3D printing as well as a preparation method and application of the SiZrOC resin, and belongs to the technical field of ceramic 3D printing. The preparation method of the SiZrOC resin comprises the following steps: 1, dissolving zirconium oxychloride in a solvent A, adding a chelating agent and triethylamine, and uniformly mixing to obtain a solution A; mixing silane, a solvent B and deionized water, and fully and uniformly mixing to obtain a solution B; step 2, dropwise adding the solution A into the solution B, and reacting for a period of time to obtain SiZrOC sol; step 3, carrying out rotary evaporation on the SiZrOC sol to obtain white turbid high-viscosity resin; and step 4, uniformly dispersing the high-viscosity resin and the organic solvent, then carrying out reduced pressure filtration to obtain clear and transparent faint yellow filtrate, and carrying out rotary evaporation treatment on the filtrate to obtain the faint yellow transparent SiZrOC resin. The ceramic part prepared by the polymer derived ceramic 3D printing technology has ultrahigh mechanical property and high temperature resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of ceramic 3D printing, and specifically relates to a SiZrOC resin capable of photocuring 3D printing, and a preparation method and application thereof. Background Art

[0002] Ceramic materials have excellent mechanical properties and high temperature resistance. Since their introduction, they have been considered as very important structural materials and have been widely used in high-tech fields such as aerospace and automobile industries. However, with the continuous development of science and technology, the performance requirements for ceramic materials are not limited to mechanical properties and high temperature resistance. Instead, there is a gradually increasing demand for the structural complexity of ceramics. However, due to the high hardness and high brittleness of ceramics themselves, traditional ceramic processing methods are difficult to manufacture ceramic parts with complex structures. Combining additive manufacturing technology with ceramic manufacturing can effectively solve the molding difficulties caused by the high hardness and high brittleness of ceramics, and provide new possibilities for the molding process of complex structural ceramics, thereby realizing the manufacturing of a series of ceramic parts such as rocket throat liners and engine parts that have extremely high requirements for high temperature resistance, mechanical properties, and structural complexity of materials. Up to now, the additive manufacturing technology of polymer-derived ceramics has become the current mainstream ceramic 3D printing technology due to its simpler processing technology. However, the mechanical strength of 3D-printed polymer-derived ceramics is difficult to compare with that of traditional industrial processed ceramics, and it cannot be used in engineering applications. Summary of the invention

[0003] In view of the problem of poor mechanical strength of existing 3D printed polymer-derived ceramics, the present invention provides a new type of SiZrOC resin that can be photocured for 3D printing and its preparation method and application. The mechanical strength of SiZrOC ceramics prepared by 3D printing polymer-derived ceramic technology is 3-5 times that of similar works at present, and while achieving high mechanical strength, other properties of ceramics are not sacrificed.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A SiZrOC resin capable of photocuring 3D printing, having the structural formula:

[0006]

[0007] In the formula, R includes one or more combinations of hydrogen, methyl, phenyl, vinyl, propyl, amino, mercapto and their derivatives; R' includes one or more combinations of acetylacetone, acrylic acid, acetic acid, dibenzoylmethane, NN-dimethylformamide, 1,2-propylene glycol; x, y, z, n, m are positive integers.

[0008] Furthermore, the molar ratio of R groups to silicon atoms is (1.0-1.8):1, and the molar ratio of Zr to silicon atoms is (1-50):100.

[0009] A method for preparing the SiZrOC resin capable of photocuring 3D printing comprises the following steps:

[0010] Step 1, dissolving zirconium oxychloride in solvent A, stirring fully at 25-50°C until completely dissolved and clear, adding a chelating agent and triethylamine, and reacting the mixed solution at 25-50°C for 0-5h to obtain solution A; mixing silane, solvent B and deionized water, stirring fully at 25-50°C until the mixture is uniform to obtain solution B;

[0011] Step 2, dripping solution A into solution B at a rate of 0.5-2 drops / second, and reacting at 50-70°C for 2-8h to obtain SiZrOC sol;

[0012] Step 3: Rotary distill the SiZrOC sol at 40-70° C. to remove solvent A and solvent B to obtain a white turbid high viscosity resin;

[0013] Step 4: fully stir or ultrasonicate the high viscosity resin and the organic solvent to completely dissolve the resin, then filter under reduced pressure to achieve solid-liquid separation to obtain a clear and transparent light yellow filtrate, and again rotary evaporate the filtrate at 40-70° C. to remove the organic solvent to obtain a light yellow and transparent SiZrOC resin.

[0014] Furthermore, in step 1, the mass ratio of the zirconium oxychloride to the solvent A is 1:(1-3); the molar ratio of the chelating agent, triethylamine and zirconium oxychloride is (0.5-2):(1-3):1; the mass ratio of the silane to the solvent B is 1:(0.5-2); the molar ratio of silane to deionized water is 1:(0.5-1.2), and the zirconium oxychloride accounts for 1-50% of the total molar number of silane.

[0015] Furthermore, in step one, the solvent A includes a combination of one or more of methanol, ethanol, and ether; the solvent B includes a combination of one or more of methanol, ethanol, isopropanol, tetrahydrofuran, and acetone; the chelating agent includes one of acetylacetone, acrylic acid, acetic acid, dibenzoylmethane, NN-dimethylformamide, and 1,2-propylene glycol; the silane includes a combination of one or more of γ-methacryloxypropyltrimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and hexamethyldisilazane.

[0016] Furthermore, in step three, the organic solvent includes a combination of one or more of acetone, chloroform, tetrahydrofuran, and xylene.

[0017] An application of the photocurable 3D-printable SiZrOC resin is to fully stir and mix the SiZrOC resin with a photosensitive group with a photoinitiator, a light absorber and a reaction diluent to obtain a SiZrOC ceramic precursor; the SiZrOC ceramic precursor is poured into a material tank of a 3D printer, and printing parameters are set to print different models, the models are kept at 80-120°C for 1-5h, 180-250°C for 1-8h, and then heated to 800-1500°C at a heating rate of 0.2-5°C / min under the protection of an inert gas, and then pyrolyzed for 0.5-4 hours and cooled naturally to obtain a uniformly shrunken SiZrOC ceramic.

[0018] Furthermore, the photoinitiator accounts for 0.1-5% of the total mass of the SiZrOC ceramic precursor; the light absorber accounts for 0.01-0.2% of the total mass of the SiZrOC ceramic precursor; and the reaction diluent accounts for 2-30% of the total mass of the SiZrOC ceramic precursor.

[0019] Furthermore, the photoinitiator includes a combination of one or more of 819, TPO, TPO-L, and 1173.

[0020] Furthermore, the reactive diluent includes one or a combination of γ-methacryloxypropyltrimethoxysilane and butyl acrylate.

[0021] Furthermore, the light absorber includes a combination of one or more of Sudan III and methyl orange.

[0022] Furthermore, the printing parameters mainly include light energy density 6-50μW / cm 2 ; Single layer exposure time 1-10s.

[0023] Furthermore, the inert gas includes nitrogen or argon.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention adopts a novel strategy to prepare SiZrOC resin, and the ceramic parts prepared by polymer-derived ceramic 3D printing technology have ultra-high mechanical properties and high temperature resistance. The zirconium source (zirconium oxychloride) used in the present invention has extremely low cost and high atomic utilization rate. The synthesis of SiZrOC resin in the present invention does not require the introduction of additional catalysts, and the method is simple and easy to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The stress-strain curve of the SiZrOC ceramic prepared in Example 1 at room temperature;

[0027] Figure 2This is the thermal weight loss curve of the SiZrOC ceramic prepared in Example 1 from room temperature to 1500°C in air;

[0028] Figure 3 This is the thermal gravimetric curve of the SiZrOC ceramic prepared in Example 2 from room temperature to 1000°C in argon. DETAILED DESCRIPTION

[0029] The technical solution of the present invention will be clearly and completely described below in conjunction with the drawings and embodiments. Obviously, the described embodiments are only part of the embodiments of the invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0030] Embodiment 1:

[0031] A preparation method and application of SiZrOC resin capable of photocurable 3D printing, comprising the following steps: dissolving 103.12 g of zirconium oxychloride in 252.56 g of ethanol, stirring and dissolving at 35°C until clear and transparent, dripping 32.04 g of acetylacetone and 64.76 g of triethylamine, reacting for 2 hours, and recording as solution A; and taking 119.21 g of γ-methacryloxypropyltrimethoxysilane, 199.70 g of methyltriethoxysilane, 237.24 g of dimethyldiethoxysilane, 560 g of ethanol, and 97.92 g of water, mixing them thoroughly, stirring evenly at 35°C, and recording as solution B. Dropping solution A into solution B at a rate of 1 drop / second, and reacting at 70°C for 4 hours after dripping to obtain SiZrOC sol. The sol system after the reaction was subjected to rotary evaporation at 50°C to remove the solvent in the system as much as possible to obtain a white turbid high-viscosity resin. 500g of tetrahydrofuran was added thereto, and the mixture was stirred vigorously until uniformly dispersed. The solution was filtered under reduced pressure to obtain a clear and transparent light yellow solution. The filtrate was subjected to rotary evaporation at 50°C to obtain 350g of light yellow, clear and transparent SiZrOC resin. Then 1.75g ​​of 819, 0.07g of Sudan III, and 17.5g of γ-methacryloxypropyltrimethoxysilane were added thereto, and the mixture was stirred thoroughly until uniformly mixed to obtain a SiZrOC ceramic precursor. The ceramic precursor was placed in a 3D printer and heated at 25μW / cm 2 The honeycomb model was printed with the parameters of light energy density and single layer 3s, and then post-processed in a high temperature oven at 80℃ for one hour and 200℃ for 6 hours. Argon was used as the protective gas, and the heating rate was increased to 1200℃ at 1℃ / min and kept at this temperature for 2 hours. After natural cooling, SiZrOC ceramic parts were obtained. The compressive strength of the ceramic is 822MPa. Figure 1 As shown. In air, there is no weight loss from room temperature to 1500℃, as shown Figure 2shown.

[0032] Embodiment 2:

[0033] A preparation method and application of SiZrOC resin capable of photocurable 3D printing, comprising the following steps: dissolving 51.56 g of zirconium oxychloride in 126.28 g of ethanol, stirring and dissolving at 35°C until clear and transparent, dripping 16.02 g of acetylacetone and 32.38 g of triethylamine, reacting for 2 hours, and recording as solution A; and taking 19.87 g of γ-methacryloxypropyltrimethoxysilane, 99.85 g of methyltriethoxysilane, 31.73 g of phenyltrimethoxysilane, 83.03 g of dimethyldiethoxysilane, 19.37 g of hexamethyldisilazane, 250 g of ethanol, and 63.36 g of water, mixing them thoroughly, stirring evenly at 35°C, and recording as solution B. Dropping solution A into solution B at a rate of 1 drop / second, and reacting at 70°C for 4 hours after dripping to obtain SiZrOC sol. The sol system after the reaction was subjected to rotary evaporation at 50°C to remove the solvent in the system as much as possible to obtain a white turbid high-viscosity resin. 300g of tetrahydrofuran was added thereto, and the mixture was stirred vigorously until uniformly dispersed. The solution was filtered under reduced pressure to obtain a clear and transparent light yellow solution. The filtrate was subjected to rotary evaporation at 50°C to obtain 140g of light yellow, clear and transparent SiZrOC resin. Then 0.70g of 819, 0.014g of Sudan III, and 14g of γ-methacryloxypropyltrimethoxysilane were added thereto, and the mixture was stirred thoroughly until uniformly mixed to obtain a SiZrOC ceramic precursor. The ceramic precursor was placed in a 3D printer and heated at 6μW / cm 2 The honeycomb model was printed with the parameters of light energy density and single layer 7s. It was then post-processed in a high temperature oven at 80°C for one hour and 200°C for six hours. Argon was used as the protective gas and the heating rate was increased to 1000°C at 1°C / min and kept at that temperature for 2 hours. After natural cooling, a SiZrOC ceramic part with a ceramic rate of 70% was obtained. Figure 3 shown.

[0034] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A SiZrOC resin capable of photocuring 3D printing, characterized in that: The structural formula is: In the formula, R includes one or more combinations of hydrogen, methyl, phenyl, vinyl, propyl, amino, mercapto and their derivatives; R' includes one or more combinations of acetylacetone, acrylic acid, acetic acid, dibenzoylmethane, NN-dimethylformamide, 1,2-propylene glycol; x, y, z, n, m are positive integers.

2. The SiZrOC resin for photocurable 3D printing according to claim 1, characterized in that: The molar ratio of R groups to silicon atoms is (1.0-1.8):1, and the molar ratio of Zr to silicon atoms is (1-50):

100.

3. A method for preparing a photocurable 3D printing SiZrOC resin according to claim 1 or 2, characterized in that: The following steps are involved: Step 1, dissolving zirconium oxychloride in solvent A, adding a chelating agent and triethylamine, and reacting the mixed solution at 25-50° C. for 0-5 h to obtain solution A; mixing silane, solvent B and deionized water, and mixing thoroughly to obtain solution B; Step 2: Add solution A dropwise into solution B, and react for a period of time to obtain SiZrOC sol; Step 3, rotary evaporating the SiZrOC sol to obtain a white turbid high viscosity resin; Step 4: Disperse the high-viscosity resin and the organic solvent evenly, and then filter under reduced pressure to obtain a clear and transparent light yellow filtrate. The filtrate is subjected to rotary evaporation to obtain a light yellow and transparent SiZrOC resin.

4. The preparation method according to claim 3, characterized in that: In step 1, the mass ratio of the zirconium oxychloride to the solvent A is 1:(1-3); the molar ratio of the chelating agent, triethylamine and zirconium oxychloride is (0.5-2):(1-3):1; the mass ratio of the silane to the solvent B is 1:(0.5-2); the molar ratio of silane to deionized water is 1:(0.5-1.2), and the zirconium oxychloride accounts for 1-50% of the molar number of silane.

5. The preparation method according to claim 3, characterized in that: In step 1, the solvent A includes a combination of one or more of methanol, ethanol, and ether; the solvent B includes a combination of one or more of methanol, ethanol, isopropanol, tetrahydrofuran, and acetone; the chelating agent includes one of acetylacetone, acrylic acid, acetic acid, dibenzoylmethane, NN-dimethylformamide, and 1,2-propylene glycol; the silane includes a combination of one or more of γ-methacryloxypropyltrimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and hexamethyldisilazane.

6. The preparation method according to claim 3, characterized in that: In step 2, the dripping rate of solution A into solution B is 0.5-2 drops / second, the reaction temperature of solution A and solution B is 50-70°C, and the reaction time is 2-8 hours.

7. The preparation method according to claim 3, characterized in that: In step three, the organic solvent includes one or more combinations of acetone, chloroform, tetrahydrofuran, and xylene.

8. The preparation method according to claim 3, characterized in that: In step 3 and step 4, the temperature of the two rotary evaporations is 40-70°C.

9. An application of the photocurable 3D printing SiZrOC resin according to claim 1 or 2, characterized in that: The SiZrOC resin is fully stirred and mixed with a photoinitiator, a light absorber and a reaction diluent to obtain a SiZrOC ceramic precursor, which is poured into a material tank of a 3D printer, and printing parameters are set to print different models. The models are pretreated in an oven, and then heated to 800-1500°C at a heating rate of 0.2-5°C / min under an inert atmosphere, and then naturally cooled after being kept warm for 0.5-4 hours to obtain uniformly shrunk SiZrOC ceramics.

10. The preparation method according to claim 9, characterized in that: The photoinitiator accounts for 0.1-5% of the total mass of the SiZrOC ceramic precursor; the light absorber accounts for 0.01-0.2% of the total mass of the SiZrOC ceramic precursor; and the reaction diluent accounts for 2-30% of the total mass of the SiZrOC ceramic precursor.

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