Biomedical silicone products, methods of making, and uses thereof

Abstract

The application discloses a biomedical organic silicon product, a preparation method and application thereof, and is characterized in that a biological organic silicon material is processed into shape through a 3D printing device, and then is subjected to debinding and sintering to obtain the biomedical organic silicon product. The biological organic silicon material comprises polyethylene glycol monomethyl methacrylate oligomer modified silicon oil and polyurethane acrylate prepolymer. The organic silicon material of the application has the advantages of maintaining low hardness (hardness is HA 35-36) and improving mechanical properties such as strength, the tensile strength of the product before sintering is as high as 1.85-2 MPa, the shear strength is as high as 1.3-1.5 MPa, the elasticity and tear resistance are high, and the 3D printing slurry of the application has good ductility, is beneficial to matching the printing device of rapid forming, the printing efficiency is as high as 30 s / layer, the precision reaches ±0.2-03 microns, and the medical application requirements are met. In addition, the application solves the resistance of the organic silicon to ultraviolet light, can be subjected to ultraviolet curing without additional ultraviolet light absorbers, and has high biocompatibility.

Description

Technical Field

[0001] This invention relates to a biomedical technology, and more particularly to a biomedical organosilicon product, a moldless preparation method for the biomedical organosilicon product, and its applications. Background Technology

[0002] Biomedical materials can be classified according to their applications into: musculoskeletal repair materials (bone, teeth, joints, tendons, etc.); soft tissue materials (skin, breast, esophagus, bladder, respiratory tract, etc.); cardiovascular system materials (artificial heart valves, blood vessels, intravascular catheters, etc.); medical membrane materials (blood purification membranes and separation membranes, gas selective permeable membranes, contact lenses, etc.); tissue adhesives and suture materials; drug delivery carrier materials; and clinical and biosensor materials. As a foundation for research on artificial organs and medical devices, biomedical materials have become an important branch of contemporary materials science. Especially with the rapid development and major breakthroughs in biotechnology, biomedical materials have become a hot topic for research and development by scientists worldwide. In recent years, numerous reports have emerged regarding medical materials and their applications in advanced medical technologies. However, overall, my country's biomedical materials field is currently in a predicament where the level of engineering and industrialization of research results is low, there is a lack of industrialization integration mechanisms, venture capital outlets are narrow, financing channels are not smooth, and there is a lack of funds for the industrialization of research results and the technological transformation of enterprises. At present, my country's biomedical materials products are developing towards large-scale, precise, personalized and intelligent directions.

[0003] Organosilicon, as a biomedical material, is a widely used polymeric elastomer in the medical industry. Its greatest advantages are its simple composition, safety, reliability, and excellent biocompatibility. Compared to other materials, it has unique advantages: compared to PVC, organosilicon achieves a very soft effect without the need for plasticizers; compared to latex, it poses no risk of allergies; and compared to thermoplastic elastomers, it exhibits more reliable temperature and pressure resistance. Furthermore, organosilicon exists in both solid and liquid states, making it suitable for various molding processes and well-suited to the complex processing requirements of the medical industry. In the medical field, it can be used to simulate tissue models, or for organ repair and implantation in the aesthetic medicine field.

[0004] Previously, silicone molding primarily employed a complex injection molding process: manufacturers had to first prepare a mold, then inject liquid silicone rubber under pressure. However, this method was too costly and only suitable for large-scale production. In the medical field, however, each patient or individual has different conditions, resulting in distinct personalized needs for silicone molding. The molding of silicone materials must be customized according to different specific requirements, and traditional molding processes are far from meeting these needs.

[0005] Silicone 3D printing, through the combination of new materials and new processes, enables entirely new part designs and moldless personalized customization. Without the use of any tools or molds, digital models can be directly converted into physical objects, thereby reducing production costs, saving production time, and significantly shortening the process cycle. At the same time, silicone 3D printing can also integrate functions into complex functional parts and prototypes. During product development, products can be quickly improved according to actual conditions, thereby improving product performance and adaptability.

[0006] However, silicone 3D printing also faces challenges. Silicone has strong resistance to ultraviolet light, and once solidified, it loses its processability and ductility, which leads to stringent requirements for the process of silicone 3D printing.

[0007] Another problem with organosilicon is that without reinforcing fillers, it has low hardness and poor mechanical properties, with a tensile strength of only 0.3-0.5 MPa, making it almost useless. After adding reinforcing fillers such as silica, the mechanical properties are improved, but the material hardness increases. This makes it less suitable for certain fields, such as the manufacture of prosthetics and orthotics, where organosilicon is used as a biomimetic material that comes into direct contact with human skin, or in household products, baby products, and health care products. In these cases, the lower the material hardness and the higher the mechanical properties, the better. Summary of the Invention

[0008] This application provides a biomedical organosilicon product, a moldless preparation method, and its application to solve the problems mentioned in the above-mentioned technical background.

[0009] The first aspect of this application is to provide a method for preparing a biomedical organosilicon product, the steps of which include:

[0010] The bio-organosilicon material is processed and shaped using 3D printing equipment, and then degreased and sintered to obtain the biomedical organosilicon product.

[0011] The bio-organosilicon material includes, and preferably comprises, polyethylene glycol monomethacrylate oligomer modified silicone oil and polyurethane acrylate prepolymer.

[0012] The raw materials for synthesizing the polyethylene glycol monomethacrylate oligomer modified silicone oil include, and preferably consist of, polyethylene glycol monomethacrylate oligomer and hydrogen-containing silicone oil.

[0013] In a preferred embodiment, the forming area of ​​the 3D printing equipment is 96mm x 54mm x 150mm.

[0014] In a preferred embodiment, the method for preparing the polyethylene glycol monomethacrylate oligomer-modified silicone oil includes the following steps:

[0015] We provide polyethylene glycol monomethacrylate oligomers, hydrogen-containing silicone oils, isopropanol solutions of Karstedt catalysts, toluene, and neutralizing agents;

[0016] The polyethylene glycol monomethacrylate oligomer and hydrogen-containing silicone oil were dissolved in toluene, and then an isopropanol solution of Karstedt catalyst was added. The mixture was heated under inert gas conditions and reacted in the dark. After the reaction was completed, the reaction product was obtained.

[0017] A neutralizing agent was added to the reaction system, and the reaction products were separated and purified to obtain polyethylene glycol monomethacrylate oligomer modified silicone oil.

[0018] The dark environment described in this application refers to the use of opaque materials to shield the reaction system and prevent light from external light sources from entering.

[0019] In a preferred embodiment, the molecular weight of the hydrogen-containing silicone oil is 2000-30000, more preferably 3600-20000, and even more preferably 4800-10000.

[0020] In a preferred embodiment, the reaction temperature of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 65-130°C, preferably 80-120°C, and more preferably 100-110°C.

[0021] In a preferred embodiment, the reaction time of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 1-10 h, preferably 3-8 h, and more preferably 5-6 h.

[0022] In a preferred embodiment, the neutralizing agent is one or more of sodium bicarbonate, sodium carbonate, potassium carbonate, and potassium bicarbonate.

[0023] In a preferred embodiment, the method for preparing the polyethylene glycol monomethacrylate oligomer includes the following steps:

[0024] We provide polyethylene glycol, methacrylic acid, sodium dodecylbenzenesulfonate, hydroquinone, and reflux water separation equipment;

[0025] Polyethylene glycol, sodium dodecylbenzenesulfonate, and hydroquinone were added to a flask, heated to a certain reaction temperature, stirred, and then methacrylic acid was added dropwise. During the reaction, a reflux separator was used to remove water from the reaction system.

[0026] After the reaction is complete, the product is discharged to obtain polyethylene glycol monomethacrylate oligomer.

[0027] In a preferred embodiment, the weight ratio of polyethylene glycol to methacrylic acid is preferably 1-3:1, more preferably 1.5-2.5:1, and even more preferably 1.8-2.3:1.

[0028] In a preferred embodiment, the weight ratio of sodium dodecylbenzenesulfonate to polyethylene glycol is 0.01-0.2:1, more preferably 0.05-0.15:1, and even more preferably 0.1-0.13:1.

[0029] In a preferred embodiment, the weight ratio of hydroquinone to polyethylene glycol is 0.01-0.2:1, more preferably 0.05-0.15:1, and even more preferably 0.1-0.13:1.

[0030] In a preferred embodiment, the method for preparing the polyurethane acrylate prepolymer includes the following steps:

[0031] We provide diisocyanates, polyethylene glycol, monohydroxy acrylates, polyurethane catalysts, and polymerization inhibitors.

[0032] Under inert gas conditions, polyethylene glycol, diisocyanate, and polyurethane catalyst are added to the reaction system and heated to the first reaction temperature T1. After the isocyanate content reaches a preset value, monohydroxy acrylate and polymerization inhibitor are added, and the reaction is heated to the second reaction temperature T2 to obtain polyurethane acrylate prepolymer.

[0033] Wherein, the molar ratio of the isocyanate group in the diisocyanate to the molar ratio of the hydroxyl groups in polyethylene glycol and monohydroxy acrylate is 1:1, that is, in the overall reaction process, n -NCO :n -OH The ratio is 1:1.

[0034] The preset value of the isocyanate content is the isocyanate content in the reaction system after the hydroxyl groups of polyethylene glycol and the isocyanate groups have completely reacted.

[0035] In a preferred embodiment, the diisocyanate is toluene diisocyanate or isophorone diisocyanate.

[0036] In a preferred embodiment, the polyethylene glycol is dehydrated.

[0037] In a preferred embodiment, the monohydroxy acrylate is one or more of trimethylolpropane diacrylate, monohydroxy epoxy acrylate, and triethoxyethyl diacrylate.

[0038] In a preferred embodiment, the polyurethane catalyst is one or more of bis(dimethylaminoethyl) ether, pentamethyldiethylenetriamine, dimethylcyclohexylamine, dibutyltin dilaurate, organobismuth, and triazine trimerizing catalyst.

[0039] In a preferred embodiment, the polymerization inhibitor is one or more of p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, and hydroquinone.

[0040] In a preferred embodiment, the molar ratio of polyethylene glycol to monohydroxy acrylate is preferably 1:1-5, more preferably 1:2-3, and even more preferably 1:2.5-2.8.

[0041] In a preferred embodiment, the weight ratio of the polyurethane catalyst to the diisocyanate is 0.1-2:1, more preferably 0.2-1:1, and even more preferably 0.5-0.8:1.

[0042] In a preferred embodiment, the weight ratio of the polymerization inhibitor to the diisocyanate is 0.01-0.2:1, more preferably 0.05-0.15:1, and even more preferably 0.1-0.13:1.

[0043] In a preferred embodiment, the first reaction temperature T1 is 60-120°C, preferably 70-100°C, and more preferably 80-90°C.

[0044] In a preferred embodiment, the second reaction temperature T2 is 60-120°C, preferably 70-100°C, and more preferably 80-90°C.

[0045] The second aspect of this application is to provide a biomedical organosilicon product obtained by the above method, wherein the product is formed by 3D printing equipment from bio-organosilicon material;

[0046] The bio-organic silicon material includes polyethylene glycol monomethacrylate oligomer modified silicone oil and polyurethane acrylate prepolymer.

[0047] The third aspect of this application is to provide an application of a biomedical organosilicon product, which is obtained by 3D printing from bio-organosilicon materials and is used in the fields of prostheses, prosthetic silicone sleeves, and human bionic models.

[0048] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0049] The biomedical organosilicon product of this application is obtained by 3D printing of bio-organosilicon material followed by debinding and sintering, achieving a moldless preparation method. The bio-organosilicon material of this application maintains the low hardness of organosilicon (hardness HA35-36) while improving mechanical properties such as strength. The tensile strength of the product before sintering is as high as 1.85-2 MPa, and the shear strength is as high as 1.3-1.5 MPa, exhibiting high elasticity and tear resistance. Furthermore, the 3D printing slurry of this application has good ductility, which is beneficial for matching with rapid prototyping printing equipment, achieving a printing efficiency of up to 30s / layer and an accuracy of ±0.2-0.3μm, thus meeting the requirements for medical applications. In addition, this application solves the problem of organosilicon's resistance to ultraviolet light, enabling ultraviolet curing without the addition of additional ultraviolet light absorbers. This avoids the biotoxicity problems caused by residues and surface migration in photocured organosilicon materials with added ultraviolet light absorbers, and the bio-organosilicon material of this application exhibits high biocompatibility. Detailed Implementation

[0050] This invention provides a biomedical organosilicon product, its preparation method, and its application. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the following examples further illustrate the invention in detail. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0051] It should be noted that the terms "first," "second," etc., used in the specification and claims of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be used interchangeably where appropriate. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to these processes, methods, products, or apparatuses.

[0052] The raw materials and equipment used in the following embodiments are:

[0053] Polyethylene glycol (Mn=200), hydroquinone, methacrylic acid, isopropanol solution of Karstedt catalyst (CAS No. 81032-58-8), toluene diisocyanate, diphenylmethane diisocyanate, 1,4-butanediol, and polymethylsiloxane (Mn=5000) were all purchased from Sigma-Aldrich.

[0054] Sodium dodecylbenzenesulfonate and sodium carbonate (AR) were purchased from Tianjin Kemei Chemical Reagent Co., Ltd. Hydrogen-containing silicone oil (Mn = 4800) was purchased from Jiangxi Yadi Chemical Co., Ltd.

[0055] Toluene and ethanol were purchased from Nanjing Runsheng Petrochemical Co., Ltd.

[0056] Nitrogen gas was purchased from Shanghai Jiajie Special Gases Co., Ltd.

[0057] Fourier transform infrared spectrometer IRAffinity-1, SHIMADZU Corporation, Japan.

[0058] Shore hardness tester, Type A, Jiangsu Tuoda Jingcheng Testing Instruments Co., Ltd.

[0059] MXL-5 tensile testing machine, Jinan Valland Instrument Co., Ltd.

[0060] Example 1:

[0061] Step 1: Preparation of polyethylene glycol monomethacrylate oligomers

[0062] 20g of polyethylene glycol, 2g of hydroquinone, and 2g of sodium dodecylbenzenesulfonate were added to a flask, heated to 110°C, and then 8.6g of methacrylic acid was added dropwise. The mixture was refluxed to remove water and reacted for 10 hours.

[0063] Infrared spectrum shows 1112cm -1 An absorption peak of -COC appears at 1300 cm⁻¹. -1 An ester group-CO- absorption peak appears at 1650 cm⁻¹. -1 A C=C absorption peak appears at 2800-3000 cm⁻¹. -1 Two broad absorption peaks of -CH3 appear at 3495 cm⁻¹. -1 The presence of a terminal hydroxyl absorption peak indicates the formation of polyethylene glycol monomethacrylate.

[0064] Step 2: Prepare polyethylene glycol monomethacrylate oligomer modified silicone oil

[0065] Nitrogen gas was purged in the flask. 20g of the polyethylene glycol monomethacrylate oligomer obtained in step 1 and 480g of hydrogen-containing silicone oil were dissolved in toluene and heated under reflux for 15min. Then, an isopropanol solution of Karstedt catalyst was added and reacted in the dark for 5 hours.

[0066] After the reaction was completed, the mixture was cooled to room temperature, sodium carbonate was added, stirred, filtered, and the solvent was removed from the filtrate to obtain modified silicone oil.

[0067] Infrared spectroscopy shows that 1650 cm -1 The absorption peak at 2162 cm⁻¹ almost disappeared. -1 The Si-H absorption peak was significantly weakened, indicating that the C=C double bond in methacrylic acid reacted with the Si-H in the hydrogen-containing silicone oil.

[0068] Step 3: Prepare polyurethane acrylate prepolymer

[0069] Under a nitrogen atmosphere, 5g of polyethylene glycol was added to a three-necked flask equipped with a stirrer, thermometer and condenser. The stirring was turned on and the temperature was raised to 120°C. The polyethylene glycol was dehydrated under reduced pressure for 2 hours.

[0070] Then, while stirring, 17.4g of toluene diisocyanate and 0.1g of zinc isooctanoate were added dropwise to the temperature below 40℃. The temperature was then raised to 80℃, and the reaction was carried out for 4 hours. Samples were taken to detect the content of isocyanate groups in the reaction system. After reaching the theoretical value, 13.6g of trimethylolpropane diacrylate and hydroquinone were added, and the temperature was raised to 80℃. After reacting for 3 hours, the mixture was discharged.

[0071] Step 4, Configuring bio-organic silica materials for 3D printing

[0072] 420g of polyethylene glycol monomethacrylate oligomer modified silicone oil obtained in step 2 and 80g of polyurethane acrylate prepolymer obtained in step 3 were mixed evenly to obtain a bio-organic silicon material for 3D printing.

[0073] Step 5, perform 3D printing.

[0074] The 3D printer selected is the XL-BS22A from Shanghai Xinlin Technology Development Co., Ltd., with a forming area of ​​96mm x 54mm x 150mm.

[0075] The bio-organosilicon material obtained in step 4 is processed using a 3D printer, and then degreased and sintered to obtain the biomedical organosilicon product of this invention.

[0076] Infrared spectroscopy shows that it is 1716 cm⁻¹ -1 The presence of an absorption peak at C=O in urethane indicates the synthesis of polyurethane (3495 cm⁻¹). -1 The near disappearance of the absorption peak at the terminal hydroxyl group indicates that the terminal hydroxyl group of the polyethylene glycol monomethacrylate oligomer modified silicone oil has copolymerized with polyurethane.

[0077] Example 2:

[0078] Step 1: Synthesis of polyethylene glycol monomethacrylate oligomers

[0079] Refer to Example 1.

[0080] Step 2: Synthesize polyethylene glycol monomethacrylate oligomer modified silicone oil

[0081] Refer to Example 1.

[0082] Step 3: Synthesize polyurethane acrylate prepolymer

[0083] Under nitrogen atmosphere, 2.6 g of 1,4-butanediol was added to a three-necked flask equipped with a stirrer, thermometer and condenser. The stirring was turned on and the temperature was raised to 120°C. The 1,4-butanediol was dehydrated under reduced pressure for 2 hours.

[0084] Then, while stirring, 25.7g of diphenylmethane diisocyanate and 0.1g of zinc isooctanoate were added dropwise to the temperature below 40℃. The temperature was then raised to 80℃, and the reaction was carried out for 4 hours. Samples were taken to detect the content of isocyanate groups in the reaction system. After reaching the theoretical value, 13.6g of trimethylolpropane diacrylate and hydroquinone were added, and the temperature was raised to 80℃. After reacting for 3 hours, the mixture was discharged.

[0085] Step 4, Configuring bio-organic silica materials for 3D printing

[0086] 420g of polyethylene glycol monomethacrylate oligomer modified silicone oil obtained in step 2 and 80g of polyurethane acrylate prepolymer obtained in step 3 were mixed evenly to obtain a bio-organic silicon material for 3D printing.

[0087] Step 5, perform 3D printing.

[0088] The 3D printer is the same as in Example 1.

[0089] The bio-organosilicon material obtained in step 4 is processed using a 3D printer, and then degreased and sintered to obtain the biomedical organosilicon product of this invention.

[0090] Infrared spectroscopy shows that it is 1718 cm⁻¹ -1 The presence of an absorption peak at C=O in urethane indicates the synthesis of polyurethane (3495 cm⁻¹). -1 The near disappearance of the absorption peak at the terminal hydroxyl group indicates that the terminal hydroxyl group of polyethylene glycol monomethacrylate has formed a copolymer with polyurethane.

[0091] Comparative Example 1:

[0092] Step 1: Preparation of polyurethane acrylate prepolymer

[0093] Refer to Example 1.

[0094] Step 2, Prepare the slurry for 3D printing

[0095] 300g of polymethylsiloxane and 200g of the polyurethane acrylate prepolymer obtained in step 2 were blended and prepared as a slurry for 3D printing.

[0096] Step 3, perform 3D printing

[0097] The 3D printer is the same as in Example 1.

[0098] The slurry obtained in step 2 is processed using a 3D printer, and then degreased and sintered to obtain a biomedical organosilicon product.

[0099] Comparative Example 2:

[0100] Step 1: Preparation of polyurethane acrylate prepolymer

[0101] Refer to Example 1.

[0102] Step 2, Prepare the slurry for 3D printing

[0103] 500g of polymethylsiloxane, 40g of the polyurethane acrylate prepolymer obtained in step 2, and 6g of hydroxyphenyl triazine UV absorption enhancer were blended to prepare a slurry for 3D printing.

[0104] Step 3, perform 3D printing

[0105] The 3D printer is the same as in Example 1.

[0106] The slurry obtained in step 2 is processed using a 3D printer, and then degreased and sintered to obtain a biomedical organosilicon product.

[0107] Comparative Example 3:

[0108] Step 1: Preparation of polyurethane acrylate prepolymer

[0109] Refer to Example 1.

[0110] Step 2, Prepare the slurry for 3D printing

[0111] 300g of polymethylsiloxane, 20g of polyethylene glycol, and 220g of the polyurethane acrylate prepolymer obtained in step 2 were blended to prepare a slurry for 3D printing.

[0112] Step 3, perform 3D printing

[0113] The 3D printer is the same as in Example 1.

[0114] The slurry obtained in step 2 is processed using a 3D printer, and then degreased and sintered to obtain a biomedical organosilicon product.

[0115] Comparative Example 4:

[0116] Step 1: Preparation of polyethylene glycol monomethacrylate oligomers

[0117] Refer to Example 1.

[0118] Step 2: Prepare polyethylene glycol monomethacrylate oligomer modified silicone oil

[0119] Refer to Example 1.

[0120] Step 3, Preparation of polyurethane-silicone copolymer

[0121] Under nitrogen atmosphere, 5g of polyethylene glycol was added to a three-necked flask equipped with a stirrer, thermometer and condenser. Stirring was started and the temperature was raised to 120°C. The polyethylene glycol was dehydrated under reduced pressure for 2 hours.

[0122] Subsequently, the temperature was lowered to below 40°C, and 17.4g of toluene diisocyanate and 0.1g of zinc isooctanoate were added dropwise while stirring. The temperature was then raised to 80°C, and the reaction was carried out for 4 hours. Samples were taken to detect the content of isocyanate groups in the reaction system. After reaching the theoretical value, 500g of the modified silicone oil and hydroquinone obtained in step 2 were added, and the temperature was raised to 80°C. After reacting for 3 hours, the material was discharged to obtain polyurethane-organic silicone copolymer.

[0123] Infrared spectroscopy shows that it is 1717 cm⁻¹ -1 The presence of an absorption peak at C=O in urethane indicates the synthesis of polyurethane (3495 cm⁻¹). -1 The near disappearance of the absorption peak of the terminal hydroxyl group indicates that the hydroxyl groups in the modified silicone oil have formed a copolymer with the polyurethane.

[0124] Step 4, Configuring bio-organic silica materials for 3D printing

[0125] The polyurethane-silicone copolymer obtained in step 3 was used as the slurry for 3D printing.

[0126] Step 5, perform 3D printing.

[0127] The slurry obtained in step 4 is processed using a 3D printer, and then degreased and sintered to obtain a biomedical organosilicon product.

[0128] Table 1. Performance Comparison of Products Obtained from Embodiments and Comparative Examples in this Application

[0129]

[0130]

[0131] It can be seen that: 1) The polyurethane acrylate prepolymer and the modified silicone oil containing polyethylene glycol in this application form a 3D printing slurry with good compatibility, which is beneficial to the dispersion of organosilicon, improves the ductility of the slurry, and thus improves the accuracy and printing efficiency of the printed product, with an accuracy of up to ±0.2-0.3μm and a printing efficiency of up to 30s / layer. 2) In the technical solution of this application, the use of polyurethane acrylate does not significantly affect the low hardness of the organosilicon material, and its hardness remains at around HA 35.5; at the same time, the use of polyurethane acrylate and the modification of polyethylene glycol can significantly improve the mechanical properties of organosilicon, such as strength, with a tensile strength of up to about 1.9MPa and a shear strength of up to about 1.4MPa. 3) Particularly unexpectedly, the organosilicon material of this application can transmit ultraviolet light very well and has good photocuring performance without the addition of a photoinitiator.

[0132] The specific embodiments of the present invention have been described in detail above, but they are merely examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, all equivalent transformations and modifications made without departing from the spirit and scope of the present invention should be covered within the scope of the present invention.

Claims

1. A method for preparing a biomedical organosilicon product, characterized in that the steps include... include: The bio-organosilicon material is processed and shaped using 3D printing equipment, and then degreased and sintered to obtain the biomedical organosilicon product. The bio-organic silicon material includes polyethylene glycol monomethacrylate oligomer modified silicone oil and polyurethane acrylate prepolymer. The raw materials for synthesizing the polyethylene glycol monomethacrylate oligomer modified silicone oil include polyethylene glycol monomethacrylate oligomer and hydrogen-containing silicone oil. The preparation method of the polyethylene glycol monomethacrylate oligomer modified silicone oil includes: We provide polyethylene glycol monomethacrylate oligomers, hydrogen-containing silicone oils, isopropanol solutions of Karstedt catalysts, toluene, and neutralizing agents; The polyethylene glycol monomethacrylate oligomer and hydrogen-containing silicone oil were dissolved in toluene, and then an isopropanol solution of Karstedt catalyst was added. The mixture was heated under inert gas conditions and reacted in the dark. After the reaction was completed, the reaction product was obtained. A neutralizing agent was added to the reaction system, and the reaction product was separated and purified to obtain polyethylene glycol monomethacrylate oligomer modified silicone oil. The method for preparing the polyethylene glycol monomethacrylate oligomer includes: We provide polyethylene glycol, methacrylic acid, sodium dodecylbenzenesulfonate, hydroquinone, and reflux water separation equipment; Polyethylene glycol, sodium dodecylbenzenesulfonate, and hydroquinone were added to a flask, heated to a certain reaction temperature, stirred, and then methacrylic acid was added dropwise. During the reaction, a reflux separator was used to remove water from the reaction system. After the reaction is complete, the product is discharged to obtain polyethylene glycol monomethacrylate oligomer.

2. The method according to claim 1, characterized in that, The molecular weight of the hydrogen-containing silicone oil is 2000-30000.

3. The method according to claim 2, characterized in that, The molecular weight of the hydrogen-containing silicone oil is 3600-20000.

4. The method according to claim 3, characterized in that, The molecular weight of the hydrogen-containing silicone oil is 4800-10000.

5. The method according to claim 1, characterized in that, The reaction temperature of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 65-130℃; the reaction time of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 1-10h.

6. The method according to claim 5, characterized in that, The reaction temperature of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 80-120℃.

7. The method according to claim 6, characterized in that, The reaction temperature of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 100-110℃.

8. The method according to claim 5, characterized in that, The reaction time of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 3-8 hours.

9. The method according to claim 8, characterized in that, The reaction time of the polyethylene glycol monomethacrylate oligomer and the hydrogen-containing silicone oil is 5-6 hours.

10. The method according to claim 1, characterized in that, The weight ratio of polyethylene glycol to methacrylic acid is 1-3:

1.

11. The method according to claim 10, characterized in that, The weight ratio of polyethylene glycol to methacrylic acid is 1.5-2.5:

1.

12. The method according to claim 11, characterized in that, The weight ratio of polyethylene glycol to methacrylic acid is 1.8-2.3:

1.

13. The method according to claim 1, characterized in that, The method for preparing the polyurethane acrylate prepolymer includes: We provide diisocyanates, polyethylene glycol, monohydroxy acrylates, polyurethane catalysts, and polymerization inhibitors. Under inert gas conditions, polyethylene glycol, diisocyanate, and polyurethane catalyst are added to the reaction system and heated to the first reaction temperature T1. After the isocyanate content reaches the preset value, monohydroxy acrylate and polymerization inhibitor are added, and the reaction is heated to the second reaction temperature T2 to obtain polyurethane acrylate prepolymer. Wherein, the molar ratio of the isocyanate group in the diisocyanate to the molar ratio of the hydroxyl groups in polyethylene glycol and monohydroxy acrylate is 1:1, that is, in the overall reaction process, n -NCO :n -OH The ratio is 1:

1.

14. The method according to claim 13, characterized in that, The molar ratio of polyethylene glycol to monohydroxy acrylate is 1:1-5.

15. The method according to claim 14, characterized in that, The molar ratio of polyethylene glycol to monohydroxy acrylate is 1:2-3.

16. The method according to claim 15, characterized in that, The molar ratio of polyethylene glycol to monohydroxy acrylate is 1:2.5-2.

8.

17. The method according to claim 13, characterized in that, The first reaction temperature T1 is 60-120℃; the second reaction temperature T2 is 60-120℃.

18. The method according to claim 17, characterized in that, The first reaction temperature T1 is 70-100℃.

19. The method according to claim 18, characterized in that, The first reaction temperature T1 is 80-90℃.

20. The method according to claim 17, characterized in that, The second reaction temperature T2 is 70-100℃.

21. The method according to claim 20, characterized in that, The second reaction temperature T2 is 80-90℃.

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