Silica gel-based material with high biocompatibility and elasticity as well as preparation method and application of silica gel-based material

Abstract

The invention discloses a silica gel-based material with high biocompatibility and elasticity as well as a preparation method and application of the silica gel-based material. The silica gel-based material with high biocompatibility and elasticity is prepared from bio-based polyurethane and polyether modified siloxane. According to the preparation method, modified polypyrrolidone is taken as a chain extender, glycidyl is taken as an end-capping reagent, a polycaprolactone prepolymer is subjected to chain extension and end capping, bio-based polyurethane is prepared, and the bio-based polyurethane is enhanced through polyether modified polysiloxane, so that the biocompatibility of a silica gel-based material is effectively improved; the tensile property and the compressive deformation resistance of the material are also improved. The silica gel-based material disclosed by the invention can be used for preparing medical catheters or thrombus simulants, and is applied to interventional operations.

Description

Technical Field

[0001] This invention relates to the field of silicone-based materials technology, specifically to a highly biocompatible and elastic silicone-based material, its preparation method, and its applications. Background Technology

[0002] Silicone, also known as silicone rubber, is a high-molecular-weight organosilicon compound mainly composed of silicon, oxygen atoms, and organic groups. In biomedical fields, silicone materials are widely used in the manufacture of various medical devices and materials, such as artificial joints, pacemakers, breast implants, medical catheters, and ventilators. The widespread use of silicone in these fields stems from its significant advantages over traditional rubber and plastics in terms of biocompatibility, chemical stability, flexibility, and ease of processing. However, to meet the demands of in vivo applications, the biocompatibility and mechanical properties of existing silicone materials still need further improvement. For example, existing silicone materials readily adsorb proteins / cells onto their surfaces, posing a risk of triggering inflammatory reactions such as capsular contracture. Furthermore, their tensile properties are poor, making them unable to withstand cyclic loads. Although studies have shown that adding reinforcing fillers such as silica and fumed silica can improve the mechanical properties of silicone materials, improper addition of these fillers can reduce tensile strength and resilience, leading to defects such as deformation and adhesion after long-term use. Summary of the Invention

[0003] The main objective of this invention is to provide a highly biocompatible and elastic silicone-based material, its preparation method, and its applications, in order to solve the technical problems existing in the prior art.

[0004] The objective of this invention can be achieved through the following technical solutions: A first aspect of the present invention provides a highly biocompatible and elastic silicone-based material, said highly biocompatible and elastic silicone-based material comprising bio-based polyurethane and polyether-modified siloxane; The preparation method of the bio-based polyurethane includes: mixing and stirring hydroxyl-terminated polycaprolactone and N,N-dimethylacetamide until the system is dissolved under an inert gas atmosphere; then adding diisocyanate and a first catalyst to the reaction system; raising the temperature of the reaction system to 80-90°C; maintaining the temperature for 20-30 min; then adding modified polypyrrolidone and glycidyl ether to the reaction system; maintaining the temperature for 35-45 min; and then performing a first post-treatment to obtain the bio-based polyurethane.

[0005] The main synthesis reaction mechanism of bio-based polyurethane is as follows:

[0006] In the formula: It is hydroxyl-terminated polycaprolactone; The simplified formula for modified polypyrrolidone; ; .

[0007] During the reaction, the first catalyst catalyzes the condensation of the isocyanate group on the diisocyanate with the hydroxyl group on the hydroxyl-terminated polycaprolactone molecule to form a long-chain polyurethane prepolymer. Modified polypyrrolidone is used as a crosslinking agent, and glycidyl ether is used as a capping agent. They are added to the reaction system at the same time to increase the crosslinking degree of the polyurethane prepolymer and form epoxy groups on the molecular chain to prepare bio-based polyurethane.

[0008] In one embodiment, the weight ratio of the bio-based polyurethane to the polyether-modified siloxane is 70-80:45-55. In the example case, if the proportion of bio-based polyurethane is relatively high, or the proportion of polyether-modified siloxane is relatively low, the following drawbacks occur: 1. The material loses the tactile feel of the polyether-modified siloxane, becoming harder and rougher. 2. Due to insufficient toughening components, the elongation at break of the material decreases, becoming more brittle and prone to cracking or even breakage during bending or stretching. 3. Surface properties deteriorate, such as decreased hydrophobicity / water resistance, increased stickiness, and potentially poor leveling properties. 4. Excessive rigid segments may lead to stress concentration during curing, affecting adhesion (especially to flexible substrates) and long-term durability.

[0009] If the proportion of polyether-modified siloxane is too high, or the proportion of bio-based polyurethane is too low, the following defects will occur: insufficient mechanical strength; excessive siloxane will migrate to the surface, forming a weak interface layer, which will severely reduce the adhesion between the coating and the substrate, leading to coating peeling; the material cannot be completely cross-linked and cured, resulting in a sticky (tacky) surface that does not feel dry; the continuity and density of the film after formation will also be affected; chemical resistance will decrease, as excessive siloxane segments will reduce the material's resistance to solvents, oils, etc.; there is a compatibility limit between the two components, and excessive addition of polyether-modified siloxane may lead to phase separation, resulting in phenomena such as "oil separation" or "fogging," causing white frost or opacity on the material surface, affecting the appearance.

[0010] In one embodiment, the ratio of the hydroxyl-terminated polycaprolactone, N,N-dimethylacetamide, the first catalyst, modified polypyrrolidone, and glycidyl ether is 20g:100mL:0.02g:4-5g:1-2g.

[0011] In some examples, an excessively high proportion of hydroxyl-terminated polycaprolactone can lead to a relative deficiency of the hard segment (xylene diisocyanate), resulting in decreased material mechanical strength; a low proportion results in insufficient soft segments, making the material brittle and reducing biocompatibility. Excessive N,N-dimethylacetamide dilutes the reaction system, reduces reaction efficiency, and increases post-processing costs; insufficient N,N-dimethylacetamide fails to fully dissolve the raw materials, leading to uneven reaction and fluctuating material properties. Excessive primary catalyst may trigger side reactions (such as over-crosslinking), causing material embrittlement; insufficient catalyst results in low catalytic efficiency, incomplete reaction, and unreacted monomer residues, reducing biocompatibility. Excessive modified polypyrrolidone leads to excessive crosslinking, decreasing material elasticity and making it prone to breakage; insufficient crosslinking weakens the material's tensile strength and resistance to compressive deformation. Excessive glycidyl ether over-terminates the material, affecting subsequent crosslinking with polyether-modified siloxanes; insufficient glycidyl ether results in insufficient termination, increased small molecule residues, and increased biocompatibility risk. Therefore, the dosage range used in this example ensures synergistic function of each component. Specifically, hydroxyl-terminated polycaprolactone provides suitable biocompatibility and flexibility, N,N-dimethylacetamide ensures full dissolution and dispersion of raw materials, the first catalyst efficiently catalyzes the reaction without excessive side reactions, modified polypyrrolidone is moderately crosslinked to improve mechanical properties and biocompatibility, and glycidyl ether effectively ends up to reduce small molecule residues. Finally, a silicone-based material with high biocompatibility and excellent mechanical properties is prepared, which better meets the application requirements of thrombosis mimics.

[0012] In one embodiment, the first catalyst may be selected, but is not limited to, dibutyltin dilaurate.

[0013] In one embodiment, the amount of diisocyanate used is 0.55-0.60 times the molar amount of hydroxyl groups in hydroxy-terminated polycaprolactone. In some examples, if the amount of diisocyanate is too low, the hydroxyl groups of hydroxy-terminated polycaprolactone cannot fully react with the isocyanate groups, leaving a large number of hydroxyl groups. This results in a low molecular weight of the polyurethane prepolymer, reduced crosslinking efficiency with modified polypyrrolidone, and insufficient crosslinking degree of the bio-based polyurethane. Consequently, the tensile strength and compressive strength of the silicone-based material are reduced, and the residual hydroxyl groups may increase the risk of small molecule release, affecting biocompatibility. Conversely, if the amount of diisocyanate is too high, the excessive isocyanate groups are prone to side reactions with the active groups of modified polypyrrolidone and the epoxy groups of glycidyl ether in the system, leading to over-crosslinking, making the material hard and brittle, and reducing the elongation at break. At the same time, the unreacted isocyanate group residue can increase biotoxicity and reduce cell survival rate, violating the design goal of high biocompatibility. The ratio range used in this embodiment is beneficial to ensure that the hydroxyl groups of hydroxyl-terminated polycaprolactone react appropriately to form a polyurethane prepolymer with a suitable molecular weight. This provides sufficient active sites for the subsequent crosslinking of modified polypyrrolidone, ensuring that the bio-based polyurethane has an ideal degree of crosslinking. This allows the silicone-based material to obtain the expected tensile strength and compression set properties, while avoiding side reactions and residue problems caused by excessive or insufficient isocyanate. This ensures that the cell survival rate of the material meets the target, thus satisfying the dual requirements of thrombosis mimicry for mechanical properties and biosafety.

[0014] In one embodiment, the diisocyanate may be, but is not limited to, xylene diisocyanate.

[0015] In one embodiment, the first post-processing includes: after the reaction is complete, the temperature of the reaction system is lowered to room temperature, anhydrous ethanol is added to the reaction system, the mixture is stirred and dispersed for 20-30 minutes, filtered, the filter cake is washed three times with anhydrous ethanol and then dried, the filter cake is transferred to a drying oven at a temperature of 70-80°C and dried to constant weight to obtain bio-based polyurethane.

[0016] In one embodiment, the method for preparing the modified polypyrrolidone includes: mixing an acrylic-cage polysilsesquioxane, vinylpyrrolidone, allyl alcohol, isopropanol solution and an initiator, raising the temperature of the reaction system to 65-75°C, maintaining the temperature for 4-6 hours, and then performing a second post-treatment to obtain the modified polypyrrolidone.

[0017] The main synthesis mechanism of modified polypyrrolidone is as follows:

[0018]

[0019] In the formula: It is an acrylic-cage-shaped polysilsesquioxane.

[0020] During the reaction, under the action of a free radical initiator, acrylic-cage polysilsesquioxane, vinylpyrrolidone and allyl alcohol undergo free radical polymerization to form modified polypyrrolidone copolymerized with polyvinylpyrrolidone and polyallyl alcohol as the core of acrylic-cage polysilsesquioxane.

[0021] In one embodiment, the ratio of the acrylic-cage-shaped polysilsesquioxane, vinylpyrrolidone, allyl alcohol, isopropanol solution and initiator is 2-3g:7-8g:1-2g:50mL:0.02g.

[0022] In some cases, excessive amounts of acrylic-cage polysilsesquioxane can lead to an overemphasis on rigid cage structures in the modified polypyrrolidone, resulting in brittle and brittle silicone-based materials with reduced elongation at break. Conversely, excessive amounts of vinylpyrrolidone can result in insufficient nano-reinforcement, weakening the tensile strength and resistance to compressive deformation. Excessive amounts of vinylpyrrolidone can lead to an overabundance of polypyrrolidone segments, making the material overly hydrophilic, hygroscopic, and excessively cross-linked. Conversely, excessive amounts of vinylpyrrolidone can reduce its resistance to protein adsorption and biocompatibility. Excessive amounts of allyl alcohol can result in excessively flexible molecular chains, reducing the material's mechanical strength. Conversely, excessive amounts of allyl alcohol can increase chain rigidity, leading to insufficient toughness. Excessive isopropanol solution can dilute the reaction system and reduce reaction efficiency. Insufficient isopropanol solution can result in incomplete dissolution of raw materials, uneven reaction, and fluctuations in material properties. Excessive amounts of initiator can easily trigger side reactions and cause uneven molecular weight distribution. Insufficient initiator solution can lead to incomplete polymerization, with residual monomers increasing the risk of biocompatibility issues. The dosage ratios used in the examples enable synergistic effects of each component. Acrylic-cage polysilsesquioxane provides appropriate nano-reinforcement, vinylpyrrolidone ensures biocompatibility and resistance to protein adsorption, allyl alcohol regulates chain flexibility, isopropanol solution ensures full dissolution and dispersion of raw materials, and the initiator efficiently initiates polymerization without excessive side reactions. The resulting modified polypyrrolidone imparts excellent properties to bio-based polyurethane, enabling silicone-based materials to achieve cell viability, tensile strength, and elongation at break, thus meeting the biocompatibility and mechanical property requirements of thrombus mimics.

[0023] In one embodiment, the isopropanol solution is preferably composed of isopropanol and N-methylpyrrolidone in a volume ratio of 5:1-2. In some examples, if the ratio is too high (too much isopropanol, too little N-methylpyrrolidone), the solubilizing effect of N-methylpyrrolidone is insufficient, making it difficult to fully dissolve raw materials such as acrylic-cage polysilsesquioxane, resulting in an uneven reaction system, incomplete polymerization of modified polypyrrolidone, and residual unreacted monomers, which affects the subsequent crosslinking effect with bio-based polyurethane and causes fluctuations in the performance of silicone-based materials. If the ratio is too low (too little isopropanol, too much N-methylpyrrolidone), the excess N-methylpyrrolidone may reduce the initiation efficiency of the initiator (such as azobisisobutyronitrile), leading to a decrease or incomplete polymerization rate. Furthermore, it is difficult to completely remove the residual N-methylpyrrolidone in subsequent post-processing, which will reduce the purity of modified polypyrrolidone and thus affect the biocompatibility and mechanical properties of silicone-based materials. In the examples, a volume ratio of 5:1-2 is used, which allows isopropanol to play the main dissolving role, while N-methylpyrrolidone efficiently assists in dissolving poorly soluble raw materials, ensuring a uniform reaction system and guaranteeing efficient and complete polymerization of modified polypyrrolidone. This allows it to fully exert its crosslinking enhancement and biocompatibility improvement effects in the preparation of bio-based polyurethane, helping silicone-based materials meet the requirements for cell survival rate, tensile strength, and compression set.

[0024] In one embodiment, the initiator includes, but is not limited to, azobisisobutyronitrile (AIBN).

[0025] In one embodiment, the second post-processing includes: after the reaction is complete, maintaining the temperature of the reaction system at 65-75°C, removing low-boiling substances by vacuum distillation, adding cyclohexane to the reaction system, filtering, washing the filter cake three times with cyclohexane and then drying it, transferring the filter cake to a drying oven at 60-70°C, and drying it to constant weight to obtain modified polypyrrolidone.

[0026] In one embodiment, the method for preparing the polyether-modified siloxane includes: mixing an amino-terminated hydrogen-containing polysiloxane, polyethylene glycol allyl methyl ether, toluene, and a second catalyst, raising the temperature of the reaction system to 75-85°C, maintaining the temperature for 4-6 hours, and then performing a third post-treatment to obtain the polyether-modified siloxane.

[0027] The main synthesis reaction mechanism of polyether-modified siloxanes is as follows:

[0028] During the reaction, the second catalyst catalyzes the hydrogen of the amino-terminated hydrogen-containing polysiloxane molecule to undergo a hydrosilylation reaction with the olefin double bond on the polyethylene glycol allyl methyl ether molecule, thereby modifying the molecular chain of the amino-terminated hydrogen-containing polysiloxane with polyethylene glycol allyl methyl ether to prepare polyether-modified siloxane.

[0029] In one embodiment, the ratio of the amino-terminated hydrogen-containing polysiloxane, polyethylene glycol allyl methyl ether, toluene, and the second catalyst is 10g:1.2-1.5g:50mL:0.02g. In some examples, when the proportion of amino-terminated hydrogen-containing polysiloxane is too high (other components are relatively insufficient), the modification of polyethylene glycol allyl methyl ether is insufficient, resulting in decreased hydrophilicity and anti-protein adsorption capacity of the material. Insufficient second catalyst leads to incomplete hydrosilylation reaction, and residual active groups affect subsequent crosslinking with bio-based polyurethane. When the proportion of polyethylene glycol allyl methyl ether is too high, excessive chain segments can easily lead to reduced mechanical strength of the material, and unreacted monomers remain. When the proportion of toluene is too high, it will dilute the reaction system and reduce reaction efficiency, while when the proportion is too low, the raw materials cannot be fully dissolved, resulting in uneven reaction. When the proportion of the second catalyst is too high, it can easily trigger side reactions, while when it is too low, the catalytic efficiency is insufficient, and the reaction is incomplete. The dosage range in this embodiment allows the amino-terminated hydrogen-containing polysiloxane as the main chain substrate to be fully modified, the polyethylene glycol allyl methyl ether to moderately modify it to ensure hydrophilicity and anti-adsorption capacity, the toluene to ensure uniform dissolution of the raw materials, and the second catalyst to efficiently catalyze the hydrosilylation reaction. The prepared polyether-modified siloxane can be well crosslinked with bio-based polyurethane.

[0030] In one embodiment, the second catalyst includes, but is not limited to, chloroplatinic acid.

[0031] In one embodiment, the third post-processing includes: after the reaction is complete, the temperature of the reaction system is reduced to room temperature, purified water is added to the reaction system, the mixture is stirred and dispersed for 20-30 minutes, the mixture is allowed to stand and separated, the organic phase is washed twice with purified water and then transferred to a rotary evaporator with a water bath temperature of 80-90℃, and low-boiling substances are removed by vacuum evaporation to obtain polyether-modified siloxane.

[0032] In one embodiment, the preparation method of the amino-terminated hydrogen-containing polysiloxane includes: mixing D4, D4H, and a third catalyst, raising the temperature of the reaction system to 85-95°C, maintaining the temperature for 2-3 hours, then adding a capping agent to the reaction system, maintaining the temperature for 1-1.5 hours, and then performing a fourth post-treatment to obtain the amino-terminated hydrogen-containing polysiloxane.

[0033] The main synthesis reaction mechanism of amino-terminated hydrogen-containing polysiloxanes is as follows:

[0034] During the reaction, the third catalyst catalyzes the ring-opening and condensation of D4 and D4H to form a long polysiloxane chain. 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, as a capping agent, undergoes bond breaking under the action of the third catalyst and then condenses with the end of the polysiloxane formed by the ring-opening condensation of D4 and D4H to form an amino-capped modification, thus preparing an amino-capped hydrogen-containing polysiloxane.

[0035] In one embodiment, the weight ratio of D4, D4H, the third catalyst, and the capping agent is 9-10:3-4:1-1.3:1-1.2. When the proportion of D4 is too high (with relatively insufficient D4H), the number of hydrogen-containing groups in the polysiloxane chain decreases, resulting in insufficient hydrosilylation reaction sites with polyethylene glycol allyl methyl ether, affecting the preparation of polyether-modified siloxanes. When the proportion of D4 is too low (with excessive D4H), the excess of hydrogen-containing groups easily leads to over-crosslinking, making the amino-capped hydrogen-containing polysiloxane hard and brittle. An excessively high proportion of the third catalyst leads to over-catalysis, causing chain segment degradation and uneven product molecular weight distribution; an excessively low proportion results in insufficient catalytic efficiency, incomplete ring-opening condensation of D4 and D4H, and increased residual monomers. An excessively high proportion of the capping agent leads to over-capping, resulting in a smaller product molecular weight and affecting subsequent modification; an excessively low proportion results in insufficient capping, residual active end groups, and increased biocompatibility risks. The dosage range used in the examples allows D4 and D4H to form a reasonable main chain structure and retain sufficient hydrogen-containing groups. The third catalyst efficiently catalyzes ring-opening condensation without side reactions, and the end-capping agent fully achieves amino end-capping. The prepared amino-capped hydrogen-containing polysiloxane can ensure the subsequent synthesis of polyether-modified siloxanes.

[0036] In one embodiment, the third catalyst may be sulfuric acid, such as sulfuric acid with a concentration of 50 wt%, but is not limited to this.

[0037] In one embodiment, the capping agent may be, but is not limited to, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane.

[0038] In one embodiment, the fourth post-processing includes: after the reaction is complete, the temperature of the reaction system is reduced to room temperature, 5 wt% sodium bicarbonate solution is added to the reaction system to adjust the pH of the system to 7, the system is allowed to stand and separate, the upper liquid is washed three times with purified water and then transferred to a rotary evaporator with a water bath temperature of 80-90℃ to remove low-boiling substances under reduced pressure to obtain amino-terminated hydrogen-containing polysiloxane.

[0039] A second aspect of the present invention provides a method for preparing the highly biocompatible and elastic silicone-based material, comprising: adding bio-based polyurethane, polyether-modified siloxane and dispersant into a mixer and mixing at a temperature of 90-100°C for 30-40 minutes to obtain the silicone-based material.

[0040] A third aspect of the invention provides the use of the aforementioned highly biocompatible and elastic silicone-based material in the preparation of medical catheters or thrombus simulants.

[0041] In one embodiment, the thrombus mimic is tubular.

[0042] A fourth aspect of the present invention also provides an interventional surgical method comprising: performing an interventional surgical procedure using a medical catheter made of the aforementioned highly biocompatible and elastic silicone-based material.

[0043] A fifth aspect of the present invention also provides an interventional surgical method, comprising: A tubular thrombus simulator is connected to the tip of the catheter used in interventional surgery. The catheter and the thrombus simulator are then inserted together into a biological blood vessel, whereby the thrombus simulator guides the catheter along the blood vessel to the lesion site. The catheter is then used to perform the corresponding surgical procedure.

[0044] Compared with the prior art, the present invention has at least the following beneficial effects: (1) This invention prepares bio-based polyurethane by extending and sealing polycaprolactone prepolymer with modified polypyrrolidone as chain extender and glycidyl as end-capping agent respectively. Hydroxyl-terminated polycaprolactone as soft segment has good biocompatibility. The introduction of acrylic-cage polysilsesquioxane improves the bioinertness of the material. Its cage structure reduces non-specific interactions with organisms. The polypyrrolidone coating on the outside has excellent blood compatibility and cell compatibility. The addition of modified polypyrrolidone further improves the hydrophilicity of the material and reduces protein adsorption on the material surface. The bio-based polyurethane is reinforced by modifying polysiloxane with polyether. The epoxy groups of glycidyl in the bio-based polyurethane can form chemical crosslinks with the amino groups on the modified polysiloxane molecular chain, reducing the risk of small molecule residues and improving the biocompatibility, tensile properties and compressive strength of silicone-based materials, preventing deformation and adhesion after long-term use.

[0045] (2) This invention uses hydroxyl-terminated polycaprolactone as the soft segment and toluene diisocyanate as the hard segment to prepare a polyurethane prepolymer of soft and hard block copolymer. Then, by modifying polypyrrolidone to increase the crosslinking degree of the polyurethane prepolymer, a bio-based polyurethane is prepared. Polycaprolactone has good biocompatibility, biodegradability, flexibility and elasticity. Toluene diisocyanate as the hard segment increases the rigidity of the polyurethane and increases the elasticity and mechanical properties of the material. Modified polypyrrolidone is used as an inorganic-organic hybrid filler. Polypyrrolidone coating enhances the hydrophilicity, biocompatibility and low protein adsorption of the material. The rigid cage structure of acrylic-cage polysilsesquioxane is used as a nano-reinforcing filler to enhance the polyurethane matrix through physical crosslinking, effectively improving the modulus and strength of the copolymer. Polypyrrolidone provides a flexible main chain to offset the rigidity of acrylic-cage polysilsesquioxane, further enhancing the biocompatibility and mechanical strength of the material.

[0046] (3) This invention also uses polyethylene glycol allyl methyl ether as a modifier to modify amino-terminated hydrogen-containing polysiloxanes. Polysiloxanes themselves have low toxicity and good blood compatibility. The polyethylene glycol allyl methyl ether segments endow the material with excellent hydrophilicity and anti-protein adsorption ability, reducing the non-specific interaction between the material surface and blood or tissue, reducing the risk of thrombosis and immune response. The high degree of rotational freedom of siloxane bonds endows the material with high elasticity and improves the elongation at break. The flexible segments of polyethylene glycol are inserted into the polyurethane matrix, reducing the friction between molecular chains and further enhancing the elongation. The siloxane main The low glass transition temperature of the chain allows it to quickly recover its deformation after compression, reducing permanent deformation. The flexible segments of polyethylene glycol form a "soft-soft" compatible structure with the siloxane network. The hydrophilicity of the polyethylene glycol modified on the polysiloxane molecular chain improves its compatibility with the bio-based polyurethane phase. Furthermore, the amino groups at the ends of the polysiloxane chain can crosslink and bond with the epoxy groups on the bio-based polyurethane molecules during high-temperature mixing, enhancing the combination of the two and further increasing the mechanical strength of the silicone-based material. The modified polysiloxane and the bio-based polyurethane form a soft-hard synergistic effect, further reducing energy loss after compression.

[0047] (4) Because the silicone-based material of the present invention has the above-mentioned excellent biocompatibility and good mechanical properties, it can be used to prepare medical catheters and has broad application prospects in interventional surgery and other fields.

[0048] (5) The thrombus simulant prepared using the silicone-based material of the present invention has intravascular migration and blood flow resistance characteristics similar to naturally formed thrombi. When implanted in an extracorporeal circulation system or in vivo, it can effectively simulate the complete migration path of a thrombus from a vascular branch upward along the blood flow direction, eventually lodging in a stenotic segment of the vessel. Furthermore, it does not induce additional thrombi or vascular irritation during migration. Simultaneously, its mechanical properties are far superior to those of a thrombus, making it suitable for interventional treatment of thrombosis in complex vessels (such as intracranial vessels). For example, during interventional surgery, the tubular thrombus simulant can be pre-loaded into the tip of a thrombus aspiration catheter before the procedure. The thrombus simulant guides the catheter along the simulated actual path of the thrombus within the vessel, quickly and accurately reaching the lesion location. This effectively shortens catheter positioning time, significantly improves catheter positioning accuracy, increases surgical efficiency, and reduces vascular damage. In particular, it can guide the catheter quickly and without damage through tortuous segments of vessels (such as the intracranial Willis circle). Detailed Implementation

[0049] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0050] In this invention, the CAS number of the acrylic-cage-shaped polysilsesquioxane is 1620202-27-8; In this invention, hydroxyl-terminated polycaprolactone was purchased from Shaanxi Xingbei Aike Biotechnology Co., Ltd., model XB-16, with a purity of 95%. In this invention, D4 is octamethylcyclotetrasiloxane, CAS number 556-67-2; In this invention, D4H is 1,3,5,7-tetramethylcyclotetrasiloxane, CAS number 2370-88-9; In this invention, polyethylene glycol allyl methyl ether was purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd. The active ingredient content is 99%, the CAS number is 27252-80-8, and the model number is HPEG2400.

[0051] Example 1 This embodiment provides a method for preparing a highly biocompatible and elastic silicone-based material, including the following steps: Step 1: Preparation of modified polypyrrolidone Isopropanol and N-methylpyrrolidone were mixed evenly at a volume ratio of 5:1 to obtain an isopropanol solution; Weigh out 10g of acrylic-cage-shaped polysilsesquioxane, 35g of vinylpyrrolidone, 5g of allyl alcohol, 250mL of isopropanol solution, and 0.1g of initiator azobisisobutyronitrile (AIBN) and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 65℃. Maintain the temperature of the reaction flask at 65℃ and remove low-boiling substances by vacuum distillation. Add 200mL of cyclohexane to the reaction system, filter, wash the filter cake three times with cyclohexane, and dry it under vacuum. Transfer the filter cake to a drying oven at 60℃ and dry it to constant weight to obtain modified polypyrrolidone.

[0052] Step 2: Preparation of bio-based polyurethane Weigh 200g of hydroxyl-terminated polycaprolactone and 1000mL of N,N-dimethylacetamide and add them to an argon-protected reaction flask. Stir until the system is dissolved. Add 0.2g of dibutyltin dilaurate to the reaction flask and stir for 10min. Calculate the amount of xylene diisocyanate to be added based on 0.55 times the molar amount of hydroxyl in the hydroxyl-terminated polycaprolactone and add it to the reaction flask. Raise the temperature of the reaction flask to 80℃ and keep it at this temperature for 20min. Add 40g of modified polypyrrolidone and 10g of glycidyl ether to the reaction flask and keep it at this temperature for 35min. Lower the temperature of the reaction flask to room temperature and add 3000mL of anhydrous ethanol to the reaction flask. Stir and disperse for 20min. Filter the mixture. Wash the filter cake three times with anhydrous ethanol and dry it. Transfer the filter cake to a drying oven at 70℃ and dry it to constant weight to obtain bio-based polyurethane.

[0053] Step 3: Preparation of amino-terminated hydrogen-containing polysiloxanes Weigh out 45g of D4, 15g of D4H, and 5g of 50wt% sulfuric acid and add them to the reaction flask. Stir the mixture and raise the temperature of the reaction flask to 85℃. Keep the mixture at this temperature for 2 hours. Add 5g of the end-capping agent 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction flask and keep the mixture at this temperature for 1 hour. Lower the temperature of the reaction flask to room temperature and add 5wt% sodium bicarbonate solution to adjust the pH of the system to 7. Allow the mixture to stand and separate the layers. Wash the upper layer of liquid three times with purified water and transfer it to a rotary evaporator with a water bath temperature of 80℃. Remove low-boiling substances by vacuum evaporation to obtain amino-terminated hydrogen-containing polysiloxane.

[0054] Step 4: Preparation of polyether-modified siloxane Weigh out 50g of amino-terminated hydrogen-containing polysiloxane, 6g of polyethylene glycol allyl methyl ether, 250mL of toluene, and 0.1g of chloroplatinic acid and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 75℃. Keep the mixture at this temperature for 4 hours. Then lower the temperature of the reaction flask to room temperature and add 200mL of purified water to the reaction flask. Stir and disperse the mixture for 20 minutes. Allow the mixture to stand and separate the liquids. Wash the organic phase twice with purified water and transfer it to a rotary evaporator with a water bath temperature of 80℃. Remove low-boiling substances by vacuum evaporation to obtain polyether-modified siloxane.

[0055] Step 5: Preparation of silicone-based materials Weigh out 70 parts by weight of bio-based polyurethane, 45 parts by weight of polyether-modified siloxane and 1 part by weight of dispersant sodium stearate, add them to a mixer at 90°C, and mix for 30 minutes to obtain silicone-based material.

[0056] Example 2 This embodiment provides a method for preparing a highly biocompatible and elastic silicone-based material, including the following steps: Step 1: Preparation of modified polypyrrolidone Isopropanol and N-methylpyrrolidone were mixed evenly at a volume ratio of 5:1.5 to obtain an isopropanol solution; Weigh out 13g of acrylic-cage-shaped polysilsesquioxane, 37g of vinylpyrrolidone, 7.5g of allyl alcohol, 250mL of isopropanol solution, and 0.1g of initiator azobisisobutyronitrile (AIBN) and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 70℃. Maintain the temperature of the reaction flask at 70℃ and remove low-boiling substances by vacuum distillation. Add 200mL of cyclohexane to the reaction system, filter, wash the filter cake three times with cyclohexane, and dry it under vacuum. Transfer the filter cake to a drying oven at 65℃ and dry it to constant weight to obtain modified polypyrrolidone.

[0057] Step 2: Preparation of bio-based polyurethane Weigh 200g of hydroxyl-terminated polycaprolactone and 1000mL of N,N-dimethylacetamide and add them to an argon-protected reaction flask. Stir until the system is dissolved. Add 0.2g of dibutyltin dilaurate to the reaction flask and stir for 13min. Calculate the amount of xylene diisocyanate to be added based on 0.57 times the molar amount of hydroxyl in the hydroxyl-terminated polycaprolactone and add it to the reaction flask. Raise the temperature of the reaction flask to 85℃ and keep it at this temperature for 25min. Add 45g of modified polypyrrolidone and 15g of glycidyl ether to the reaction flask and keep it at this temperature for 40min. Lower the temperature of the reaction flask to room temperature and add 3000mL of anhydrous ethanol to the reaction flask. Stir and disperse for 25min. Filter the mixture. Wash the filter cake three times with anhydrous ethanol and dry it. Transfer the filter cake to a drying oven at 75℃ and dry it to constant weight to obtain bio-based polyurethane.

[0058] Step 3: Preparation of amino-terminated hydrogen-containing polysiloxanes Weigh out 47g of D4, 17g of D4H, and 6g of 50wt% sulfuric acid and add them to the reaction flask. Stir the mixture and raise the temperature of the reaction flask to 90℃. Maintain the temperature for 2.5h. Add 5.5g of the end-capping agent 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction flask and maintain the temperature for 1.3h. Lower the temperature of the reaction flask to room temperature and add 5wt% sodium bicarbonate solution to adjust the pH of the system to 7. Allow the mixture to stand and separate the layers. Wash the upper layer of liquid three times with purified water and transfer it to a rotary evaporator with a water bath temperature of 85℃. Remove low-boiling substances by vacuum evaporation to obtain amino-terminated hydrogen-containing polysiloxane.

[0059] Step 4: Prepare polyether-modified siloxane.

[0060] Weigh out 50g of amino-terminated hydrogen-containing polysiloxane, 6.8g of polyethylene glycol allyl methyl ether, 250mL of toluene, and 0.1g of chloroplatinic acid and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 80℃. Keep the mixture at this temperature for 5 hours. Then lower the temperature of the reaction flask to room temperature and add 200mL of purified water to the reaction flask. Stir and disperse the mixture for 25 minutes. Allow the mixture to stand and separate the liquids. Wash the organic phase twice with purified water and transfer it to a rotary evaporator with a water bath temperature of 85℃. Remove low-boiling substances by vacuum evaporation to obtain polyether-modified siloxane.

[0061] Step 5: Preparation of silicone-based materials Weigh out 75 parts by weight of bio-based polyurethane, 50 parts by weight of polyether-modified siloxane and 1.5 parts by weight of calcium stearate dispersant, add them to a mixer at 95°C, and mix for 35 minutes to obtain silicone-based material.

[0062] Example 3 This embodiment provides a method for preparing a highly biocompatible and elastic silicone-based material, including the following steps: Step 1: Preparation of modified polypyrrolidone Isopropanol and N-methylpyrrolidone were mixed evenly at a volume ratio of 5:2 to obtain an isopropanol solution; Weigh out 15g of acrylic-cage-shaped polysilsesquioxane, 40g of vinylpyrrolidone, 10g of allyl alcohol, 250mL of isopropanol solution, and 0.1g of initiator azobisisobutyronitrile (AIBN) and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 75℃. Maintain the temperature of the reaction flask at 75℃ and remove low-boiling substances by vacuum distillation. Add 200mL of cyclohexane to the reaction system, filter, wash the filter cake three times with cyclohexane, and dry it under vacuum. Transfer the filter cake to a drying oven at 70℃ and dry it to constant weight to obtain modified polypyrrolidone.

[0063] Step 2: Preparation of bio-based polyurethane Weigh 200g of hydroxyl-terminated polycaprolactone and 1000mL of N,N-dimethylacetamide and add them to an argon-protected reaction flask. Stir until the system is dissolved. Add 0.2g of dibutyltin dilaurate to the reaction flask and stir for 15min. Calculate the amount of xylene diisocyanate to be added based on 0.60 times the molar amount of hydroxyl in the hydroxyl-terminated polycaprolactone and add it to the reaction flask. Keep the reaction flask temperature at 90℃ for 30min. Add 50g of modified polypyrrolidone and 20g of glycidyl ether to the reaction flask and keep the reaction temperature at 45min. Lower the reaction flask temperature to room temperature and add 3000mL of anhydrous ethanol. Stir and disperse for 30min. Filter the mixture. Wash the filter cake three times with anhydrous ethanol and dry it. Transfer the filter cake to a drying oven at 80℃ and dry it to constant weight to obtain bio-based polyurethane.

[0064] Step 3: Preparation of amino-terminated hydrogen-containing polysiloxanes Weigh out 50g of D4, 20g of D4H, and 6.5g of 50wt% sulfuric acid and add them to the reaction flask. Stir the mixture and raise the temperature of the reaction flask to 95℃. Keep the reaction at this temperature for 3 hours. Add 6g of the end-capping agent 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction flask and keep the reaction at this temperature for 1.5 hours. Lower the temperature of the reaction flask to room temperature and add 5wt% sodium bicarbonate solution to adjust the pH of the system to 7. Allow the mixture to stand and separate the layers. Wash the upper layer of liquid three times with purified water and transfer it to a rotary evaporator with a water bath temperature of 90℃. Remove low-boiling substances by vacuum evaporation to obtain amino-terminated hydrogen-containing polysiloxane.

[0065] Step 4: Prepare polyether-modified siloxane.

[0066] Weigh out 50g of amino-terminated hydrogen-containing polysiloxane, 7.5g of polyethylene glycol allyl methyl ether, 250mL of toluene, and 0.1g of chloroplatinic acid and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 85℃. Keep the mixture at this temperature for 6 hours. Then lower the temperature of the reaction flask to room temperature and add 200mL of purified water to the reaction flask. Stir and disperse the mixture for 30 minutes. Allow the mixture to stand and separate the liquids. Wash the organic phase twice with purified water and transfer it to a rotary evaporator with a water bath temperature of 90℃. Remove the low-boiling substances by vacuum evaporation to obtain polyether-modified siloxane.

[0067] Step 5: Preparation of silicone-based materials Weigh out the following components by weight: 80 parts of bio-based polyurethane, 55 parts of polyether-modified siloxane, and 2 parts of zinc stearate dispersant. Add them to a mixer at 100°C and mix for 40 minutes to obtain a silicone-based material.

[0068] Example 4 This embodiment provides a method for preparing a tubular thrombus mimic, including the following steps: The silicone-based material prepared in Example 1 was added to a twin-screw extruder. The extrusion parameters were set as follows: barrel zone 1 temperature 105℃, zone 2 temperature 110℃, and die head temperature 108℃. A tubular extrusion die with an aperture of about 4mm (suitable for coronary arteries) was selected, the die gap was controlled to be about 0.8mm, and the extrusion rate was about 6mm / s. After extrusion, the tubular preform was placed in an 85℃ forced-air drying oven for annealing for about 2 hours, and then naturally cooled to room temperature. It was then cut into tubular thrombus simulators with a diameter of about 4mm, a wall thickness of about 0.8mm, and a length of about 20mm.

[0069] Example 5 The difference between this embodiment and embodiment 4 is that the silicone-based material used is the product prepared in embodiment 2.

[0070] Example 6 The difference between this embodiment and embodiment 4 is that the silicone-based material used is the product prepared in embodiment 3.

[0071] Comparative Example 1 The difference between this comparative example and Example 3 is that vinylpyrrolidone was not added in step one.

[0072] Comparative Example 2 The difference between this comparative example and Example 3 is that, in step one, acrylic-cage-shaped polysilsesquioxane was not added.

[0073] Comparative Example 3 The difference between this comparative example and Example 3 is that step four is omitted, and the amino-terminated hydrogen-containing polysiloxane in step three is used instead of the polyether-modified polysiloxane in step five.

[0074] Performance testing: The effect of the silicone-based materials prepared in Examples 1-3 and Comparative Examples 1-3 on cell viability was determined according to the CMTT cytotoxicity test in Appendix of GB / T16886.5-2017 "Biological evaluation of medical devices - Part 5: In vitro cytotoxicity test".

[0075] Referring to the standard GB / T528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber", the silicone-based materials prepared in Examples 1-3 and Comparative Examples 1-3 were prepared into dumbbell-shaped specimens, and the tensile strength and elongation at break of the specimens were measured.

[0076] Referring to standard GB / T7759.1-2015 "Determination of compression set of vulcanized or thermoplastic rubber - Part 1: Under normal and high temperature conditions", the silicone-based materials prepared in Examples 1-3 and Comparative Examples 1-3 were used to prepare cylindrical specimens with a diameter of 13.0±0.5 mm and a height of 6.3±0.3 mm. The compression set of the specimens was measured at 40°C. The specific test data are shown in Table 1 below.

[0077] Referring to YY / T0993-2015 "Evaluation Method for Hemodynamic Performance of Cardiovascular Implants", the tubular thrombus simulants prepared in Examples 4-6 were respectively connected to the extracorporeal circulation system and injected with 4.0 mPa. The blood simulation solution (37℃) was used. The constant flow pump was adjusted to gradually increase the blood flow velocity from 0.1 m / s to 0.5 m / s. After each gradient was stabilized for 5 min, the pressure loss ΔP at both ends of the simulation was measured by a pressure sensor. The blood flow velocity v at different axial positions (L=0 mm, 5 mm, 10 mm, 15 mm, 20 mm) of the simulation was measured by an ultrasonic blood flow velocimeter. The wall shear stress WSS was calculated (formula: WSS=4μv / d, where μ is the blood viscosity and d is the inner diameter of the simulation).

[0078] Simultaneously, the hemodynamic performance of fresh venous thrombi was tested using the same method. The method for preparing the venous thrombus is as follows: a non-anticoagulated venous blood sample from a healthy volunteer was quickly injected into the interlayer cavity of a double-layer silicone tube mold. The mold cavity is annular, with an inner diameter of approximately 4 mm, a ring diameter of approximately 1 mm, and a length of approximately 250 mm. The two ends of the mold cavity were then sealed. The double-layer silicone tube mold was then bent into a silicone tube ring and quickly placed on the plexiglass disk of the thrombus detector. The instrument was started to rotate the silicone tube ring at a speed of approximately 16 rpm, and the temperature inside the instrument was maintained at approximately 37°C. After rotating for approximately 15 minutes, the silicone tube ring was removed, and the blood sample was gently poured onto filter paper. One end of the thrombus was gently held with ophthalmic forceps and placed on the filter paper, and a section of approximately 20 mm in length was cut off as the test sample.

[0079] To verify the accuracy of the path simulation of the thrombus simulants, in vitro hemodynamic tests were performed on the tubular thrombus simulants prepared in Examples 4-6 and the aforementioned fresh venous thrombus samples. The test conditions completely simulated the human physiological environment (temperature 37°C, blood simulation fluid viscosity 4.0 mPa). The blood flow velocity was 0.1-0.5 m / s, corresponding to the blood flow state from vein to artery in the human body. The test equipment was a constant flow pump, pressure sensor and ultrasonic blood flow velocimeter. Numerical simulation was performed using ANSYS Fluent 2023 R1 software. Specific data and linear analysis are shown in Table 2 below.

[0080] Table 1 - Performance Test Data of Silicone-Based Material Samples

[0081] Table 2 - Performance Test Data of Thrombus Simulator Samples

[0082] Comparative analysis of the data in Table 1: The silicone-based material prepared by this invention exhibited a cell viability of 99.6% in the MTT cytotoxicity test, a tensile strength of 12.5 MPa, an elongation at break of 361.0%, and a compression set of 2.1%. All performance test data were superior to the comparative example. This demonstrates that the present invention, by using modified polypyrrolidone as a chain extender and glycidyl ether as a capping agent to extend and cap the polycaprolactone prepolymer, prepares a bio-based polyurethane. Further reinforcement of the bio-based polyurethane with polyether-modified polysiloxane not only effectively improves the biocompatibility of the silicone-based material but also enhances its tensile and compression set properties, making it suitable for preparing medical catheters (such as neurointerventional catheters).

[0083] Analyze the data in Table 2: The linear relationship between pressure loss and blood flow velocity: In the range of 0.1-0.5 m / s, ΔP increases strictly linearly with v (R²≥0.993), and the regression equation is ΔP=1.25v+0.03, which is in perfect agreement with the linear law of ΔP-v in real human thrombi (R²≥0.98). This proves that the simulated object can accurately reflect the influence of thrombi on blood flow resistance and thus simulate the hemodynamic changes in thrombus development. The attenuation law of blood flow velocity along the axial direction: the velocity from the inlet end (the starting position of thrombus formation) to the outlet end (the position of thrombus retention) of the thrombus simulator decreases linearly from 0.5 m / s to 0.15 m / s, and the attenuation equation has R²≥0.993, which is consistent with the physiological characteristic of 'blood flow velocity decreases linearly with the increase of thrombus length' during human thrombus migration, and can accurately reproduce the actual development path of thrombus. Wall shear stress safety: The average WSS is 1.8-2.5 Pa, which is within the tolerance range of human vascular endothelial cells (1.0-4.0 Pa), with no risk of vascular damage, ensuring the biosafety of thrombus mimics when guided in vivo.

[0084] Based on the properties of the aforementioned thrombus mimics, they can be applied in interventional procedures. Specifically, some embodiments of the present invention provide an interventional procedure method comprising: connecting any one of the thrombus mimics prepared in Examples 4-6 to the tip of an interventional catheter; then inserting the catheter and the thrombus mimic together into a biological blood vessel, allowing the thrombus mimic to guide the catheter along the blood vessel to the lesion location; and then using the catheter to perform a corresponding surgical operation, such as thrombectomy. In this way, by utilizing the guiding effect of the thrombus mimic during surgery, the catheter positioning time can be shortened, and the risk of vascular intimal injury can be reduced.

[0085] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A highly biocompatible and elastic silicone-based material, characterized in that, The highly biocompatible and elastic silicone-based materials include bio-based polyurethane and polyether-modified siloxanes. The preparation method of the bio-based polyurethane includes: mixing and stirring hydroxyl-terminated polycaprolactone and N,N-dimethylacetamide until the system is dissolved under an inert gas atmosphere; then adding diisocyanate and a first catalyst to the reaction system; raising the temperature of the reaction system to 80-90°C; maintaining the temperature for 20-30 min; then adding modified polypyrrolidone and glycidyl ether to the reaction system; maintaining the temperature for 35-45 min; and then performing a first post-treatment to obtain the bio-based polyurethane.

2. The highly biocompatible and elastic silicone-based material according to claim 1, characterized in that, The weight ratio of the bio-based polyurethane to the polyether-modified siloxane is 70-80:45-55.

3. The highly biocompatible and elastic silicone-based material according to claim 1, characterized in that, The ratio of hydroxyl-terminated polycaprolactone, N,N-dimethylacetamide, the first catalyst, modified polypyrrolidone, and glycidyl ether is 20g:100mL:0.02g:4-5g:1-2g. The first catalyst comprises dibutyltin dilaurate. The amount of diisocyanate is 0.55-0.60 times the molar amount of hydroxyl groups in the hydroxyl-terminated polycaprolactone. The diisocyanate is xylene diisocyanate.

4. The highly biocompatible and elastic silicone-based material according to claim 1, characterized in that, The method for preparing the modified polypyrrolidone includes: mixing acrylic-cage polysilsesquioxane, vinylpyrrolidone, allyl alcohol, isopropanol solution and initiator, raising the temperature of the reaction system to 65-75℃, maintaining the temperature for 4-6 hours, and then performing a second post-treatment to obtain the modified polypyrrolidone.

5. The highly biocompatible and elastic silicone-based material according to claim 4, characterized in that, The ratio of the acrylic-cage-shaped polysilsesquioxane, vinylpyrrolidone, allyl alcohol, isopropanol solution and initiator is 2-3g:7-8g:1-2g:50mL:0.02g. The isopropanol solution is composed of isopropanol and N-methylpyrrolidone in a volume ratio of 5:1-2. The initiator includes azobisisobutyronitrile.

6. The highly biocompatible and elastic silicone-based material according to claim 1, characterized in that, The preparation method of the polyether-modified siloxane includes: mixing amino-terminated hydrogen-containing polysiloxane, polyethylene glycol allyl methyl ether, toluene and a second catalyst, raising the temperature of the reaction system to 75-85℃, maintaining the temperature for 4-6 hours, and then performing a third post-treatment to obtain the polyether-modified siloxane.

7. The highly biocompatible and elastic silicone-based material according to claim 6, characterized in that, The ratio of amino-terminated hydrogen-containing polysiloxane, polyethylene glycol allyl methyl ether, toluene, and the second catalyst is 10g:1.2-1.5g:50mL:0.02g, and the second catalyst includes chloroplatinic acid.

8. The highly biocompatible and elastic silicone-based material according to claim 6, characterized in that, The preparation method of the amino-terminated hydrogen-containing polysiloxane includes: mixing D4, D4H and a third catalyst, raising the temperature of the reaction system to 85-95℃, maintaining the temperature for 2-3 hours, then adding a capping agent to the reaction system, maintaining the temperature for 1-1.5 hours, and then performing a fourth post-treatment to obtain the amino-terminated hydrogen-containing polysiloxane.

9. A method for preparing the highly biocompatible and elastic silicone-based material according to any one of claims 1-8, characterized in that, include: Bio-based polyurethane, polyether-modified siloxane, and dispersant are added to a mixer and mixed at 90-100℃ for 30-40 minutes to obtain the silicone-based material.

10. The use of the highly biocompatible and elastic silicone-based material according to any one of claims 1-8 in the preparation of medical catheters.

11. The use of the highly biocompatible and elastic silicone-based material according to any one of claims 1-8 in the preparation of thrombus mimics.

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