CN115340674A - Silicone resin for rapid 3D printing and preparation method and application thereof - Google Patents
Silicone resin for rapid 3D printing and preparation method and application thereof Download PDFInfo
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- CN115340674A CN115340674A CN202210992095.4A CN202210992095A CN115340674A CN 115340674 A CN115340674 A CN 115340674A CN 202210992095 A CN202210992095 A CN 202210992095A CN 115340674 A CN115340674 A CN 115340674A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses silicone resin for rapid 3D printing and a preparation method and application thereof, and belongs to the technical field of 3D printing materials. The preparation method of the silicone resin for rapid 3D printing comprises the following steps: s1, preparing monodisperse nano-silica particles: hydrolyzing the silicon source water solution to obtain a solution A; s2, preparation of a silicone resin prepolymer: adding glacial acetic acid and an alcohol aqueous solution into the solution A, adding a silicon source and a silane coupling agent with carbon-carbon double bonds, and carrying out hydrolysis and copolymerization reaction to prepare an active prepolymer; after cooling, adding a saturated sodium bicarbonate solution, and carrying out liquid separation, drying and rotary evaporation to obtain a silicone resin prepolymer; s3, preparation of silicone resin for rapid 3D printing: and (3) uniformly mixing the photoinitiator with the silicone prepolymer in the S2 to obtain the resin for 3D printing. The invention achieves the aim of rapid printing by adjusting the proportion of the silicon source and the silane coupling agent with carbon-carbon double bonds and improving the curing speed of the silane coupling agent.
Description
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to silicone resin for rapid 3D printing and a preparation method and application thereof.
Background
The light curing (SLA) 3D printing is that a photoinitiator is added into a liquid photosensitive resin material and is stirred and put into a 3D printer, the shape of a three-dimensional target part is divided into a plurality of plane layers by utilizing the accumulation molding of the material, the liquid photosensitive resin is scanned by ultraviolet rays with certain wavelength, the scanned liquid photosensitive resin of each layer is partially cured and molded, the liquid photosensitive resin which is not scanned and irradiated is still liquid, and finally the liquid photosensitive resin is accumulated into a required target object. 3D prints and has advantages such as production efficiency is high, energy-conservation, environmental protection.
The liquid photosensitive resin material for 3D printing comprises epoxy acrylate, polyurethane acrylate, polyester acrylate, organic silicon polymer and the like. Epoxy acrylate has the advantages of high hardness, low shrinkage rate and the like, but has high viscosity, is not favorable for molding, and has high brittleness of molded products. The urethane acrylate photo-cured product thereof has excellent chemical resistance, but the wide application is limited due to high cost. Polyester acrylates also have the advantages of low viscosity and low cost, but have poor properties after curing and are prone to shrinkage.
The organic silicon polymer is a high molecular compound with siloxane as a main chain and a side chain as an organic group connected with silicon, and has excellent performances of high and low temperature resistance, aging resistance, low surface tension and the like because the organic silicon polymer takes the siloxane as the main chain.
The prior art discloses a polyurethane modified organic silicon resin, polyurethane is introduced into organic silicon, the mechanical strength of the organic silicon is improved, but no relevant improvement is made on the low viscosity and the quick printing performance of the organic silicon resin.
Disclosure of Invention
The invention aims to solve the technical problems of high viscosity and low printing speed of the existing silicone resin for rapid 3D printing, and provides a preparation method of the silicone resin for rapid 3D printing.
Another object of the present invention is to provide a silicone resin for rapid 3D printing.
The invention further aims to provide application of the silicone resin for rapid 3D printing in preparation of materials for 3D printing.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, preparing monodisperse nano-silica particles: hydrolyzing the silicon source water solution to obtain a solution A;
s2, preparation of a silicone resin prepolymer: adding glacial acetic acid and an alcohol aqueous solution into the solution A, adding a silicon source and a silane coupling agent with carbon-carbon double bonds, and carrying out hydrolysis and copolymerization reaction to prepare an active prepolymer; cooling, separating, drying and rotary steaming to obtain a silicone resin prepolymer;
s3, preparation of the silicone resin for rapid 3D printing: uniformly mixing a photoinitiator with the silicone prepolymer in the S2 to obtain silicone for rapid 3D printing;
wherein in S1, the silicon source is tetraethoxysilane and/or methyl orthosilicate;
in S2, the molar ratio of the silicon source to the silane coupling agent is (1-7) to 5;
the molar ratio of the sum of the molar ratio of the organic siloxane in the silicon source and the silane coupling agent to the water is 1 (1.5-2.5);
the hydrolysis reaction temperature is 40-55 ℃, and the pH value of the solution A is 3-4;
the invention improves the solid content by synthesizing monodisperse nano-silica particles, introduces a photocuring group with a carbon-carbon double bond through hydrolyzing and copolymerizing a silicon source and a silane coupling agent with the carbon-carbon double bond under an acidic condition to synthesize an active prepolymer, forms an interpenetrating network (IPN) by hydrolyzing the silicon source and the silane coupling agent with the carbon-carbon double bond, and forms a new more stable network by crosslinking the interpenetrating network, thereby improving the chemical and physical properties of the resin and improving the curing speed of the resin to achieve the aim of rapid printing.
After absorbing light energy under an ultraviolet lamp source, photoinitiator molecules generate excited singlet states or excited triplet states through photolysis to generate active free radicals, and polymerization reaction is initiated. The silicone resin prepolymer is sensitive to purple light due to the structure of conjugated double bonds, absorbs the purple light to generate n-pi-electron transition to form a singlet excited state, and is subjected to intersystem crossing to an excited triplet state to capture free radicals generated in a photoinitiator auxiliary agent through a cracking reaction to form primary free radicals. The free radical attack initiates polymerization reaction, the formed primary free radical attacks the silicone prepolymer, so that double bonds in the silicone prepolymer are attacked and opened to form new free radicals to trigger chain reaction, the unsaturated double bonds in the silicone prepolymer have high activity and high photocuring efficiency, and the result of rapid curing is achieved.
Wherein, the glacial acetic acid is used for catalyzing the hydrolysis of the silicon source.
After the active prepolymer is prepared, the product can be made neutral by neutralizing the excess acid in the reaction by adding a saturated sodium bicarbonate solution.
Wherein, in S1, the catalyst for hydrolyzing the silicon source is one or more of L-lysine, arginine and L-lysine hydrochloride.
Preferably, the molar ratio of the silicon source to the silane coupling agent in S2 is (3-5): 5.
Preferably, in S2, the reaction temperature is 45-50 ℃.
Preferably, in S2, the reaction pH is 3.3 to 3.4.
Preferably, the silane coupling agent is one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane or gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
Preferably, the photoinitiator is one or more of 2,4, 6-trimethylbenzoylphenylphosphinic acid ethyl ester, 2-hydroxy-2-methyl-1-phenyl acetone or 1-hydroxycyclohexyl phenyl ketone.
The photoinitiator needs to match the photocuring conditions, and ethyl 2,4, 6-trimethylbenzoylphenylphosphinate (TPO-L) can react at a wavelength of 405 nm.
1-hydroxycyclohexyl phenyl ketone (Irgacure 184) can be reacted at a wavelength of 246, 280 or 333 nm.
2-hydroxy-2-methyl-1-phenylacetone (Darocur 1173) can be reacted at a wavelength of 365 nm.
Preferably, the alcohol in the alcohol aqueous solution is one or more of isopropanol, methanol or ethanol.
The boiling point of isopropanol, methanol or ethanol is low, which is beneficial to removal in reduced pressure rotary evaporation.
The invention also provides the silicone resin for rapid 3D printing prepared by the preparation method.
Preferably, the viscosity of the silicone resin for rapid 3D printing is 20 to 70cps.
The invention also protects the application of the silicone resin for rapid 3D printing in the preparation of materials for 3D printing.
The silicone resin for rapid 3D printing prepared by the invention has excellent performances of low viscosity, high solid content, rapid printing and the like, the viscosity of the prepared photocuring resin is 20-70 cps, the printing speed is high, the shortest single-layer exposure time is 1s, and the critical exposure is less than 5.5mJ/cm 2 . The method can be widely applied to preparation of materials for 3D printing.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of silicone resin for rapid 3D printing, which improves solid content by synthesizing monodisperse nano-silica particles, introduces a photocuring group with a carbon-carbon double bond by hydrolyzing and copolymerizing a silicon source and a silane coupling agent with a carbon-carbon double bond under an acidic condition to synthesize an active prepolymer, hydrolyzes the silicon source and the silane coupling agent with the carbon-carbon double bond to form an interpenetrating network (IPN), and crosslinks the interpenetrating network to form a new more stable network, thereby improving the chemical and physical properties of the resin and improving the curing speed of the resin to achieve the purpose of rapid printing.
The silicone resin for rapid 3D printing prepared by the invention has excellent performances of low viscosity, high solid content, rapid printing and the like, the viscosity of the prepared photocuring resin is 20-70 cps, the printing speed is high, the shortest single-layer exposure time is 1s, and the critical exposure is less than 5.5mJ/cm 2 . The method can be widely applied to preparation of materials for 3D printing.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the embodiments in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, preparing monodisperse nano silicon dioxide particles: adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the speed of 1000rpm at the temperature of 60 ℃, then adding 20.8g of Tetraethoxysilane (TEOS) into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, preparation of a silicone resin prepolymer: firstly, 1.7g of glacial acetic acid, 22.83g of isopropanol and 13.68g of deionized water are put into a solution A, the solution A is mechanically stirred at the room temperature of 270-290 rpm for 5-6 min to ensure that the pH value of the solution A is 3.3, then 4.16g of TEOS is added into the solution A, 24.84g of gamma-methacryloxypropyltrimethoxysilane (KH 570) is added into a constant pressure funnel and is dripped into the solution, the solution A is mechanically stirred at the speed of 270-290 rpm and is hydrolyzed under the acid condition of 45 ℃ for condensation for 4h, after a reaction system is cooled to the room temperature, a saturated bicarbonate solution is added into a four-mouth flask and is uniformly stirred, then the mixture is transferred into a separating funnel, deionized water and dichloromethane are used for shaking to uniformly separate out a water phase, deionized water is used for washing for multiple times until an organic phase is neutral, and then the solvent and water are removed by rotary evaporation under reduced pressure to obtain a colorless and transparent silicone resin prepolymer;
s3, preparation of silicone resin for rapid 3D printing: adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator in the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
wherein in S2, the molar ratio of the sum of the molar ratios of the organic siloxane in the silicon source and the silane coupling agent to the water is 1.
Example 2
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the speed of 1000rpm at the temperature of 60 ℃, then adding 20.8g of TEOS into the single-neck flask, stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, 2.9g of glacial acetic acid, 32.44g of isopropanol and 19.44g of deionized water are placed into the solution A, and mechanical stirring is carried out at the room temperature of 270-290 rpm/min for 5-6 min, so that the pH value of the solution A is 3.3. Adding 12.48g TEOS into the solution A, adding 24.84g KH570 into a constant-pressure funnel, dropwise adding into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing under 45 ℃ acid condition for condensation for 4h, cooling the reaction system to room temperature, adding a saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and then carrying out reduced-pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
wherein in S2, the molar ratio of the sum of the molar ratios of the organic siloxane in the silicon source and the silane coupling agent to the water is 1.
Example 3
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to enable the pH value of the solution A to be 3.4. Adding 20.8g TEOS into the solution A, adding 24.84g KH570 into a constant-pressure funnel, dropwise adding into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing under 45 ℃ acid condition for condensation for 4h, cooling the reaction system to room temperature, adding a saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and then carrying out reduced-pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
wherein, in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1.
Example 4
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the speed of 1000rpm at the temperature of 60 ℃, then adding 20.8g of TEOS into the single-neck flask, stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, putting 2.4g of glacial acetic acid, 51.67g of isopropanol and 30.96g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to ensure that the pH value of the solution A is 3.3. Adding 29.12g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 45 ℃ under an acidic condition for condensation for 4h, adding a saturated bicarbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly separating out a water phase by using deionized water and dichloromethane through oscillation, washing the solution with deionized water for multiple times until an organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
wherein, in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1.
Example 5
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to enable the pH value of the solution A to be 3.4. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 40 ℃ under an acidic condition for condensation for 4h, adding a saturated hydrogen carbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicon resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1;
in contrast to example 3, the reaction temperature in S2 was 40 ℃.
Example 6
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to ensure that the pH value of the solution A is 5. Adding 20.8g TEOS into the solution A, adding 24.84g KH570 into a constant-pressure funnel, dropwise adding into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing under 45 ℃ acid condition for condensation for 4h, cooling the reaction system to room temperature, adding a saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and then carrying out reduced-pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the organic siloxane in the silicon source and the silane coupling agent to water is 1;
in contrast to example 3, solution A in S2 had a pH of 5.
Comparative example 1
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to ensure that the pH value of the solution A is 3.4. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 45 ℃ under an acidic condition for condensation for 4h, adding a saturated hydrogen carbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicon resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to water was 1.
Comparative example 2
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 37.8g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to ensure that the pH value of the solution A is 3.4. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 45 ℃ under an acidic condition for condensation for 4h, adding a saturated hydrogen carbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicon resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to water was 1.
Comparative example 3
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the speed of 1000rpm at the temperature of 60 ℃, then adding 20.8g of TEOS into the single-neck flask, stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to ensure that the pH value of the solution A is 3.4. Adding 20.8g TEOS into the solution A, adding 24.84g KH570 into a constant-pressure funnel, dropwise adding into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing under 65 ℃ acid condition for condensation for 4h, cooling the reaction system to room temperature, adding a saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and then carrying out reduced-pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the organic siloxane in the silicon source and the silane coupling agent to water is 1;
in contrast to example 3, the reaction temperature in S2 was 65 ℃.
Comparative example 4
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to ensure that the pH value of the solution A is 3.4. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 85 ℃ under an acidic condition for condensation for 4h, adding a saturated hydrogen carbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicon resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1;
in contrast to example 3, the reaction temperature in S2 was 85 ℃.
Comparative example 5
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to enable the pH value of the solution A to be 3.4. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 30 ℃ under an acidic condition for condensation for 4h, adding a saturated bicarbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly shaking with deionized water and dichloromethane to separate out a water phase, washing with deionized water for multiple times until the organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1;
in contrast to example 3, the reaction temperature in S2 was 30 ℃.
Comparative example 6
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of formic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to enable the pH value of the solution A to be 3.4. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 45 ℃ under an acidic condition for condensation for 4h, adding a saturated hydrogen carbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicon resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1;
in contrast to example 3, the catalyst in S2 was formic acid.
Comparative example 7
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the speed of 1000rpm at the temperature of 60 ℃, then adding 20.8g of TEOS into the single-neck flask, stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of hydrochloric acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to enable the pH value of the solution A to be 3.4. Adding 20.8g TEOS into the solution A, adding 24.84g KH570 into a constant-pressure funnel, dropwise adding into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing under 45 ℃ acid condition for condensation for 4h, cooling the reaction system to room temperature, adding a saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and then carrying out reduced-pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1;
in contrast to example 3, the catalyst in S2 was hydrochloric acid.
Comparative example 8
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to ensure that the pH value of the solution A is 2. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant-pressure funnel, dropwise adding the TEOS into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing at 45 ℃ under an acidic condition for condensation for 4h, adding a saturated hydrogen carbonate solution into a four-neck flask after the reaction system is cooled to room temperature, uniformly stirring, transferring the solution into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and performing reduced pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicon resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1;
unlike example 3, solution a in S2 had a pH of 2.
Comparative example 9
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the speed of 1000rpm at the temperature of 60 ℃, then adding 20.8g of TEOS into the single-neck flask, stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to enable the pH value of the solution A to be 6. Adding 20.8g TEOS into the solution A, adding 24.84g KH570 into a constant-pressure funnel, dropwise adding into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing under 45 ℃ acid condition for condensation for 4h, cooling the reaction system to room temperature, adding a saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and then carrying out reduced-pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratios of the organic siloxane in the silicon source and the silane coupling agent to water is 1;
in contrast to example 3, solution A in S2 had a pH of 6.
Comparative example 10
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3g of L-lysine into a single-neck flask, then adding deionized water into an oil bath kettle, stirring for 12min at the temperature of 60 ℃ and the rpm of 1000, then adding 20.8g of TEOS into the single-neck flask, and stirring for 12h at the constant temperature of 60 ℃ until the solution is clear, and marking as a solution A;
s2, firstly putting 2.23g of glacial acetic acid, 42.06g of isopropanol and 25.2g of deionized water into the solution A, and mechanically stirring at the room temperature of 270-290 rpm/min for 5-6 min to enable the pH value of the solution A to be 3.4. Adding 2.08g TEOS into the solution A, adding 24.84g KH570 into a constant-pressure funnel, dropwise adding into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing under 45 ℃ acid condition for condensation for 4h, cooling the reaction system to room temperature, adding a saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring into a separating funnel, uniformly shaking by deionized water and dichloromethane to separate out a water phase, washing by deionized water for multiple times until an organic phase is neutral, and then carrying out reduced-pressure rotary evaporation to remove the solvent and water to obtain a colorless and transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphinate photoinitiator of the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone resin for rapid 3D printing;
wherein, in S2, the molar ratio of the sum of the molar ratios of the silicon source and the organosiloxane in the silane coupling agent to the water is 1.
Result detection
By means of a Haake rotational rheometer and an infrared spectrometer (Magna 360, nicolet, USA), 1 H NMR and characterization of viscosity, double bond conversion, double bond content and critical exposure, and curing depth were performed on the photosensitive resins of each example and comparative example at 405nm under an ultraviolet lamp source.
A series of silicone prepolymers were synthesized by varying the molar ratio between Tetraethylorthosilicate (TEOS) and a silane coupling agent (KH 570) under acidic conditions, by real time FIIR, haake rotational rheology, 1 H NMR and ultraviolet light source 405nm to test the double bond conversion rate, viscosity, double bond content, critical exposure and curing depth, wherein the smaller the required critical exposure, namely 3D printing siliconThe lower the intensity of light to which the resin is cured, the faster the printing speed.
The specific detection results are described in table 1 below:
TABLE 1
As can be seen from the data, the silicone resin for rapid 3D printing prepared by the invention has excellent performances of low viscosity, high solid content, rapid printing and the like, the viscosity of the prepared photocuring resin is 20-70 cps, the printing speed is high, the shortest single-layer exposure time is 1s, and the critical exposure is less than 5.5mJ/cm 2 . The preparation method can be widely applied to preparation of materials for 3D printing.
The double bond content, the double bond conversion rate and the like of the silicone resin for rapid 3D printing prepared by the invention can influence the curing depth and the irradiation light intensity required by curing. Under the same irradiation light intensity, the deeper the curing depth, the better the curing effect and the high double bond conversion rate. The lower the critical exposure, the lower the intensity of the radiation required for curing, and the faster the printing speed.
As can be seen from example 3 and comparative examples 1 and 2, when the molar ratio of the deionized water to the silane coupling agent in comparative example 1 is 1, the process of synthesizing the silicone resin is not easy to control, and when the amount of the deionized water is less, the silane coupling agent is not completely hydrolyzed, and the product is layered and is easy to gel; in comparative example 2, when the molar ratio of deionized water to silane coupling agent was 3, an excess amount of deionized water in the process of synthesizing silicone resin resulted in the formation of silicone resin having a relatively high molecular weight, which resulted in a macromolecular cyclic structure, which was easily gelled, and had poor storage stability.
As can be seen from example 3 and comparative examples 3 to 5, in comparative example 3, when the reaction temperature is 65 ℃, the viscosity of the synthesized silicone resin is too high, and the product silicone resin has poor storage stability and is easy to gel; in comparative example 4, when the reaction temperature was 85 ℃, the silicone resin was easily gelled during synthesis, and the prepared silicone resin was high in viscosity and poor in leveling property, which was not favorable for photocuring 3D printing. In comparative example 5, the reaction temperature was 30 ℃, the reaction time was too long, and the reaction was not hydrolyzed by ordinary infrared test, resulting in a low double bond content and conversion rate, high critical exposure and shallow curing depth.
As can be seen from example 3 and comparative examples 6 and 7, in comparative example 6, the viscosity of the silicone resin synthesized by selecting formic acid as a catalyst is too high, the storage stability is inferior to that of glacial acetic acid as a catalyst, and the leveling property of the resin is not good, which is not favorable for photocuring 3D printing. In comparative example 7, hydrochloric acid was selected as a catalyst to synthesize silicone resin, which was agglomerated during the post-treatment, and thus the catalytic effect was strong, the polycondensation reaction was severe, the cross-linked network was dense, and the silicone resin was agglomerated to form white floccules, which did not allow post-treatment and 3D printing.
As can be seen from the example 3, the comparative example 8 and the comparative example 9, in the comparative example 8, when the pH value of the reaction is 1 to 3, the acidity in the reaction system is too high, the polycondensation reaction can be carried out when the hydrolysis is not reacted, the speed is too high in the process of synthesizing the silicone resin, the silicone resin is easy to gel, the appearance of the product is milky white, and the 3D printing cannot be carried out; in comparative example 9, the hydrolysis and polycondensation reactions were accelerated at a reaction pH of 6, but the photocuring kinetics of the silicone prepolymer product tested, and example 3 was more suitable for 3D printing than example 3.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of silicone resin for rapid 3D printing is characterized by comprising the following steps:
s1, preparing monodisperse nano silicon dioxide particles: hydrolyzing the silicon source water solution to obtain a solution A;
s2, preparing a silicone resin prepolymer: adding glacial acetic acid and an alcohol aqueous solution into the solution A, adding a silicon source and a silane coupling agent with carbon-carbon double bonds, and carrying out hydrolysis and copolymerization reaction to prepare an active prepolymer; cooling, separating, drying and rotary steaming to obtain a silicone resin prepolymer;
s3, preparation of silicone resin for rapid 3D printing: uniformly mixing a photoinitiator with the silicone prepolymer in the S2 to obtain silicone for rapid 3D printing;
wherein in S1, the silicon source is tetraethoxysilane and/or methyl orthosilicate;
in S2, the molar ratio of the silicon source to the silane coupling agent is (1-7) to 5;
the molar ratio of the sum of the molar ratios of the organic siloxane in the silicon source and the silane coupling agent to the water is 1 (1.5-2.5);
the hydrolysis reaction temperature is 40-55 ℃, and the pH value of the solution A is 3-4.
2. The method for preparing the silicone resin for rapid 3D printing according to claim 1, wherein the molar ratio of the silicon source to the silane coupling agent in S2 is (3-5): 5.
3. The method for preparing the silicone resin for rapid 3D printing according to claim 1, wherein the reaction temperature in S2 is 45 to 50 ℃.
4. The method for preparing the silicone resin for rapid 3D printing according to claim 1, wherein the pH of the solution a in S2 is 3.3 to 3.4.
5. The method for preparing the silicone resin for rapid 3D printing according to claim 1, wherein the silane coupling agent is one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, or gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
6. The method for preparing silicone resin for rapid 3D printing according to claim 1, wherein the photoinitiator is one or more of ethyl 2,4, 6-trimethylbenzoylphenylphosphinate, 2-hydroxy-2-methyl-1-phenylpropanone, or 1-hydroxycyclohexylphenylketone.
7. The method for preparing the silicone resin for rapid 3D printing according to claim 1, wherein the alcohol in the alcohol aqueous solution is one or more of isopropanol, methanol or ethanol.
8. The silicone resin for rapid 3D printing prepared by the method for preparing a silicone resin for rapid 3D printing according to any one of claims 1 to 7.
9. The silicone resin for rapid 3D printing according to claim 8, wherein the silicone resin for rapid 3D printing has a viscosity of 20 to 70cps.
10. Use of the silicone resin for rapid 3D printing according to claim 9 for preparing a material for 3D printing.
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