CN115340674B - Silicon resin for rapid 3D printing and preparation method and application thereof - Google Patents

Silicon resin for rapid 3D printing and preparation method and application thereof Download PDF

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CN115340674B
CN115340674B CN202210992095.4A CN202210992095A CN115340674B CN 115340674 B CN115340674 B CN 115340674B CN 202210992095 A CN202210992095 A CN 202210992095A CN 115340674 B CN115340674 B CN 115340674B
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silicone resin
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solution
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CN115340674A (en
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王磊
刘晓暄
向洪平
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Guangdong University of Technology
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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
    • 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
    • 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
    • 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
    • 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

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Abstract

The invention discloses a 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 the rapid 3D printing comprises 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, adding saturated sodium bicarbonate solution, separating, drying and steaming to obtain silicone resin prepolymer; s3, preparing silicone resin for rapid 3D printing: and (3) uniformly mixing the photoinitiator with the silicone resin prepolymer in the step (S2) to obtain the resin for 3D printing. The invention can achieve the purpose of rapid printing by adjusting the proportion of the silicon source and the silane coupling agent with carbon-carbon double bond and improving the curing speed.

Description

Silicon resin for rapid 3D printing and preparation method and application thereof
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to a silicone resin for rapid 3D printing, a preparation method and application thereof.
Background
The photo-curing (SLA) 3D printing is to add a photo-initiator into a liquid photosensitive resin material, stir the liquid photosensitive resin material, put the material into a 3D printer, divide the shape of a three-dimensional target part into a plurality of plane layers by using accumulation molding of the material, scan the liquid photosensitive resin by ultraviolet rays with a certain wavelength, partially cure and mold the scanned liquid photosensitive resin of each layer, and finally accumulate the liquid photosensitive resin which is not scanned and irradiated 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 includes epoxy acrylate, urethane acrylate, polyester acrylate, silicone polymer, and the like. The epoxy acrylate has the advantages of high hardness, low shrinkage rate and the like, but has larger viscosity, is unfavorable for molding, and has large brittleness of molded products. Polyurethane acrylic esters have excellent chemical resistance properties as photo-cured products, but have high cost to limit wide application. Polyester acrylates also have the advantages of low viscosity and low cost, but have poor properties after curing and are prone to shrinkage.
The organosilicon polymer is a high molecular compound with siloxane as a main chain and an organic group connected with silicon as a side chain, and has excellent performances of high and low temperature resistance, aging resistance, low surface tension and the like due to the fact that the organosilicon polymer is with the siloxane as the main chain.
The prior art discloses a polyurethane modified silicone resin, wherein polyurethane is introduced into silicone, so that the mechanical strength of the silicone is improved, but the low viscosity and the rapid printing performance of the silicone resin are not improved.
Disclosure of Invention
The invention aims to overcome the defects of high viscosity and low printing speed of the traditional 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.
It is a further object of the present invention to provide the use of a silicone resin for rapid 3D printing in the preparation of a material for 3D printing.
The above object of the present invention is achieved by the following technical scheme:
a preparation method of silicone resin for rapid 3D printing comprises 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 liquid, drying and spin-evaporating to obtain silicone resin prepolymer;
s3, preparing silicone resin for rapid 3D printing: uniformly mixing the photoinitiator with the silicone resin prepolymer in the step S2 to obtain the silicone resin for rapid 3D printing;
in S1, the silicon source is ethyl orthosilicate and/or methyl orthosilicate;
s2, the mol ratio of the silicon source to the silane coupling agent is (1-7) 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 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;
according to the invention, the solid content is improved by synthesizing monodisperse nano silicon dioxide particles, the active prepolymer is synthesized by hydrolysis and copolymerization of a silicon source and a silane coupling agent with a carbon-carbon double bond under an acidic condition, a photo-curing group with the carbon-carbon double bond is introduced, the silicon source and the silane coupling agent with the carbon-carbon double bond form an interpenetrating network (IPN) after hydrolysis, and the interpenetrating network is crosslinked to form a new more stable network, so that the chemical and physical properties of the resin are improved, and the curing speed is increased to achieve the aim of rapid printing.
The photoinitiator molecule absorbs light energy under an ultraviolet lamp source, and generates active free radicals through photolysis to generate an excited singlet state or an excited triplet state, so as to initiate polymerization. The silicon 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 the singlet excited state is converted into an excited triplet state through intersystem leaping, so that the photoinitiator auxiliary agent is abstracted to form a primary free radical through free radicals generated in a cleavage reaction. The primary free radical formed by the free radical attack initiates the polymerization reaction to attack the silicone resin prepolymer, so that double bonds in the silicone resin prepolymer are attacked and opened to form new free radicals, the chain reaction is triggered, the unsaturated double bonds in the silicone resin prepolymer have high activity, the photo-curing efficiency is high, and the rapid curing result is achieved.
Wherein, glacial acetic acid is used for catalyzing the hydrolysis of a silicon source.
After the preparation of the active prepolymer, the product can be neutralized by adding saturated sodium bicarbonate solution to neutralize the excess acid in the reaction.
In S1, the catalyst for hydrolyzing the silicon source is one or more of L-lysine, arginine and L-lysine hydrochloride.
Preferably, in S2, the molar ratio of the silicon source to the silane coupling agent is (3-5): 5.
Preferably, in S2, the reaction temperature is 45 to 50 ℃.
Preferably, in S2, the reaction pH is 3.3 to 3.4.
Preferably, the silane coupling agent is one or more of gamma-methacryloxypropyl trimethoxy silane, gamma-aminopropyl triethoxy silane or gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane.
Preferably, the photoinitiator is one or more of ethyl 2,4, 6-trimethylbenzoylphenyl phosphinate, 2-hydroxy-2-methyl-1-phenylpropion or 1-hydroxycyclohexyl phenyl ketone.
The photoinitiator needs to be matched with the photo-curing condition, and the 2,4, 6-trimethyl benzoyl phenyl phosphinic acid ethyl ester (TPO-L) can react at the wavelength of 405 nm.
1-hydroxycyclohexyl phenyl ketone (Irgacure 184) may react at a wavelength of 246, 280 or 333 nm.
2-hydroxy-2-methyl-1-phenylpropion (Darocur 1173) may react at a wavelength of 365 nm.
Preferably, the alcohol in the alcohol aqueous solution is one or more of isopropanol, methanol or ethanol.
The isopropanol, methanol or ethanol has a low boiling point, and is favorable for removal during reduced pressure rotary evaporation.
The invention also protects the silicon resin for the rapid 3D printing, which is prepared by the preparation method of the silicon resin for the rapid 3D printing.
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 preparing a material for 3D printing.
The silicone resin for rapid 3D printing prepared by the invention has the excellent performances of low viscosity, high solid content, rapid printing and the like, the viscosity of the prepared photo-curing resin is 20-70 cps, the printing speed is high, the single-layer exposure time is 1s at the shortest, and the critical exposure is less than 5.5mJ/cm 2 . Can be widely applied to 3DPreparation of printing material.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a silicon resin for rapid 3D printing, which improves solid content by synthesizing monodisperse nano silicon dioxide particles, synthesizes an active prepolymer by hydrolysis and copolymerization of a silicon source and a silane coupling agent with a carbon-carbon double bond under an acidic condition, introduces a photo-curing group with the carbon-carbon double bond, and forms an interpenetrating network (IPN) by the silicon source and the silane coupling agent with the carbon-carbon double bond after hydrolysis, and the interpenetrating network is crosslinked to form a new more stable network, thereby improving chemical and physical properties of the resin and improving curing speed of the resin to achieve the purpose of rapid printing.
The silicone resin for rapid 3D printing prepared by the invention has the excellent performances of low viscosity, high solid content, rapid printing and the like, the viscosity of the prepared photo-curing resin is 20-70 cps, the printing speed is high, the single-layer exposure time is 1s at the shortest, and the critical exposure is less than 5.5mJ/cm 2 . Can be widely applied to the preparation of 3D printing materials.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, preparing monodisperse nano silicon dioxide particles: adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of Tetraethoxysilane (TEOS) into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and marking as solution A;
s2, preparing 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, 270-290 rpm/min of mechanical stirring is carried out for 5-6 min at room temperature, 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-methacryloxypropyl trimethoxysilane (KH 570) is added into a constant pressure funnel and is added into the solution dropwise, 270-290 rpm of mechanical stirring is carried out under the acidic condition of 45 ℃ for hydrolysis-condensation for 4h, after the reaction system is cooled to room temperature, saturated bicarbonate solution is added into a four-mouth flask for uniform stirring, then the solution is transferred into a separating funnel, deionized water and methylene dichloride are used for shaking and uniform water phase separation, deionized water is used for cleaning for many times until the organic phase is neutral, and then the solvent and water are removed by decompression and spin to obtain colorless transparent silicone prepolymer;
s3, preparing silicone resin for rapid 3D printing: adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and carrying out ultrasonic treatment to obtain the silicone for rapid 3D printing;
wherein in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2.
Example 2
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as solution A;
s2, 2.9g of glacial acetic acid, 32.44g of isopropanol and 19.44g of deionized water are put into the solution A, and the solution A is mechanically stirred for 5-6 min at 270-290 rpm/min at room temperature, so that the pH value of the solution A is 3.3. Adding 12.48g of TEOS into the solution A, adding 24.84g of KH570 into a constant pressure funnel, dropwise adding the solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
wherein in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2.
Example 3
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
wherein in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2.
Example 4
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as solution A;
s2, 2.4g of glacial acetic acid, 51.67g of isopropanol and 30.96g of deionized water are put into the solution A, and the solution A is mechanically stirred for 5 to 6 minutes at 270 to 290rpm/min at room temperature, so that the pH value of the solution A is 3.3. 29.12g of TEOS is added into solution A, 24.84g of KH570 is added into a constant pressure funnel and is added into the solution dropwise, 270-290 rpm/min of mechanical stirring is carried out for hydrolysis-condensation for 4 hours under the acidic condition of 45 ℃, the reaction system is cooled to room temperature, saturated bicarbonate solution is added into a four-neck flask to be stirred uniformly, then the mixture is transferred into a separating funnel, deionized water and methylene dichloride are used for shaking and uniformly separating out water phase, deionized water is used for cleaning for many times until an organic phase is neutral, and then the solvent and water are removed by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
wherein in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2.
Example 5
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 40 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the reaction temperature was 40 ℃.
Example 6
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature to enable the pH value of the solution A to be 5. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant pressure funnel, dropwise adding the solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the pH of solution A was 5.
Comparative example 1
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
wherein, unlike example 3, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water in S2 is 1:1.
Comparative example 2
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
wherein, unlike example 3, in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water was 1:3.
Comparative example 3
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 65 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the reaction temperature was 65 ℃.
Comparative example 4
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 85 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the reaction temperature was 85 ℃.
Comparative example 5
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 30 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the reaction temperature was 30 ℃.
Comparative example 6
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the catalyst was formic acid.
Comparative example 7
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature 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 solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the catalyst was hydrochloric acid.
Comparative example 8
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature to enable the pH value of the solution A to be 2. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant pressure funnel, dropwise adding the solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the pH of solution A was 2.
Comparative example 9
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature to enable the pH value of the solution A to be 6. Adding 20.8g of TEOS into the solution A, adding 24.84g of KH570 into a constant pressure funnel, dropwise adding the solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2;
unlike example 3, in S2, the pH of solution A was 6.
Comparative example 10
A preparation method of silicone resin for rapid 3D printing comprises the following steps:
s1, adding 0.3-g L-lysine into a single-neck flask, adding deionized water into an oil bath kettle, stirring at 1000rpm for 12min at 60 ℃, adding 20.8g of TEOS into the single-neck flask, stirring at constant temperature at 60 ℃ for 12h until the solution is clear, and recording as 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 for 5-6 min at 270-290 rpm/min at room temperature to enable the pH value of the solution A to be 3.4. Adding 2.08g of TEOS into the solution A, adding 24.84g of KH570 into a constant pressure funnel, dropwise adding the solution into the solution, mechanically stirring at 270-290 rpm/min, hydrolyzing-condensing for 4 hours under the acidic condition of 45 ℃, cooling the reaction system to room temperature, adding saturated bicarbonate solution into a four-neck flask, uniformly stirring, transferring the mixture into a separating funnel, uniformly separating out a water phase by shaking with deionized water and methylene dichloride, washing the water phase with deionized water for a plurality of times until an organic phase is neutral, and then removing the solvent and the water by reduced pressure rotary evaporation to obtain colorless transparent silicone resin prepolymer;
s3, adding 2wt.% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphinate photoinitiator into the silicone prepolymer, and performing ultrasonic treatment to obtain the silicone for rapid 3D printing;
wherein in S2, the molar ratio of the sum of the molar ratio of the silicon source and the organosiloxane in the silane coupling agent to water is 1:2.
Result detection
Through a Hark rotary rheometer and an infrared spectrometer (Magna 360 type, nicolet Inc. of U.S.A.), a measuring device, 1 H NMR and characterization of the photosensitive resins of each example and comparative example for viscosity, double bond conversion, double bond content, critical exposure, and cure depth at 405nm with uv light source.
Synthesis of a series of silicone prepolymers by varying the molar ratio between tetraethyl orthosilicate (TEOS) and a silane coupling agent (KH 570) under acidic conditions by real time FIIR, hark rotational rheology, 1 The lower the critical exposure required, i.e. the lower the illumination intensity at which the 3D printed silicone resin is cured, the faster the printing speed, the H NMR and the testing of its double bond conversion, viscosity, double bond content, and critical exposure and curing depth at 405nm with uv light source.
Specific test results are shown in table 1 below:
TABLE 1
From the data, the silicon resin for rapid 3D printing prepared by the invention has the excellent performances of low viscosity, high solid content, rapid printing and the like, the viscosity of the prepared photo-curing resin is 20-70 cps, the printing speed is high, the single-layer exposure time is 1s at the shortest, and the critical exposure quantity is highLess than 5.5mJ/cm 2 . Can be widely applied to the preparation of materials for 3D printing.
The double bond content, the double bond conversion rate and the like of the silicon resin for rapid 3D printing, which is 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 is, the better the curing effect is, and the double bond conversion rate is high. The lower the critical exposure, the lower the irradiation intensity required for curing, and the faster the printing speed.
As can be seen from example 3, comparative example 1 and comparative example 2, in comparative example 1, when the molar ratio of deionized water to the silane coupling agent is 1, the process of synthesizing the silicone resin is not easy to control, and when the amount of deionized water is small, the silane coupling agent is not completely hydrolyzed, and the product is layered and is easy to gel; when the molar ratio of deionized water to the silane coupling agent in comparative example 2 is 3, the excess of deionized water in the process of synthesizing the silicone resin can generate silicone resin with larger molecular weight, generate a macromolecular cyclic structure, is easy to gel, and has poor storage stability.
As can be seen from example 3 and comparative examples 3 to 5, in comparative example 3, the viscosity of the synthesized silicone resin was too high at a reaction temperature of 65℃and the storage stability of the product silicone resin was poor and gelation was easy; in comparative example 4, when the reaction temperature is 85 ℃, the synthetic silicone resin is easy to gel in the process, and the prepared silicone resin has high viscosity and poor leveling property, and is unfavorable for photocuring 3D printing. In comparative example 5, when the reaction temperature is 30 ℃, the reaction time is too long, and the double bond content and the conversion rate are low due to the fact that the reaction time is basically unhydrolyzed through the common infrared test, the critical exposure is high, and the curing depth is shallow.
As can be seen from example 3 and comparative examples 6 and 7, in comparative example 6, the viscosity of the synthesized silicone resin was too high by selecting formic acid as a catalyst, the storage stability was poor with respect to glacial acetic acid as a catalyst, and the leveling property of the resin was poor, which was unfavorable for photo-curing 3D printing. In comparative example 7, hydrochloric acid was selected as a catalyst to form clusters in the post-treatment of the synthesized silicone resin, the catalytic effect was strong, the polycondensation reaction was severe, the cross-linking network was dense to cause the clusters to form white floccules, the post-treatment could not be performed, and the 3D printing could not be performed.
As can be seen from example 3, comparative example 8 and comparative example 9, in 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 occurs without the hydrolysis, the speed is too high in the process of synthesizing the silicone resin, the silicone resin is easy to gel, and the appearance of the product is milky and cannot be subjected to 3D printing; in comparative example 9, the hydrolysis and polycondensation reaction can be accelerated at a pH of 6, but the photo-curing kinetics test of the resultant silicone prepolymer is more suitable for 3D printing than in example 3.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (8)

1. The preparation method of the silicone resin for rapid 3D printing is characterized by comprising the following steps of:
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 liquid, drying and spin-evaporating to obtain silicone resin prepolymer;
s3, preparing silicone resin for rapid 3D printing: uniformly mixing the photoinitiator with the silicone resin prepolymer in the step S2 to obtain the silicone resin for rapid 3D printing;
in S1, the silicon source is at least one of tetraethoxysilane or tetramethylsilicate;
s2, the mol ratio of the silicon source to the silane coupling agent is (1-7) 5;
the molar ratio of the sum of the number of moles of the alkoxy groups connected with silicon in the silicon source and the number of moles of the alkoxy groups connected with silicon in the silane coupling agent to 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 photoinitiator is one or more of ethyl 2,4, 6-trimethylbenzoylphenyl phosphinate, 2-hydroxy-2-methyl-1-phenylpropion or 1-hydroxycyclohexyl phenyl ketone;
the alcohol in the alcohol water solution is one or more of isopropanol, methanol or ethanol.
2. The method for preparing a silicone resin for rapid 3D printing according to claim 1, wherein the molar ratio of the silicon source and the silane coupling agent in S2 is (3 to 5): 5.
3. The method for preparing a 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 silicone resin for rapid 3D printing according to claim 1, wherein in S2, the pH value of the solution a is 3.3 to 3.4.
5. The method for preparing a silicone resin for rapid 3D printing according to claim 1, wherein the silane coupling agent is γ -methacryloxypropyl trimethoxysilane.
6. 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 5.
7. The rapid 3D printing silicone resin of claim 6, wherein the rapid 3D printing silicone resin has a viscosity of 20 to 70cps.
8. Use of the silicone resin for rapid 3D printing of claim 6 for preparing a material for 3D printing.
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