WO2014056336A1 - 一种仿生牙种植体及其制备方法 - Google Patents

一种仿生牙种植体及其制备方法 Download PDF

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Publication number
WO2014056336A1
WO2014056336A1 PCT/CN2013/079112 CN2013079112W WO2014056336A1 WO 2014056336 A1 WO2014056336 A1 WO 2014056336A1 CN 2013079112 W CN2013079112 W CN 2013079112W WO 2014056336 A1 WO2014056336 A1 WO 2014056336A1
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Prior art keywords
layer
polyurethane
titanium dioxide
dental implant
bionic
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English (en)
French (fr)
Inventor
张利
王立军
李玉宝
龚梅
胡盼
胡静
李继华
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SI CHUAN UNIV
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SI CHUAN UNIV
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

Definitions

  • the invention belongs to the field of dental implants, and particularly relates to a pure titanium dental implant with a surface covered with a low modulus periodontal membrane and a preparation method thereof. Background technique
  • the natural tooth is suspended in the jaw bone through the periodontal ligament.
  • the tooth When the tooth is stressed, the external force is evenly transmitted and dispersed through the periodontal membrane to the jaw bone, thereby causing a physiological response to the external force of the periodontal tissue; and the osseointegrated dental implant It is rigidly connected with the jaw bone, and the two are in direct contact with the lack of periodontal membrane.
  • the elastic modulus of the dental implant When the elastic modulus of the dental implant is inconsistent with the elastic modulus of the jaw, the impact energy generated by the impact denture of the implant denture is through the dental implant. Directly transmitted to the surrounding bone tissue, which tends to cause stress concentration of the bone tissue around the dental implant, causing the surrounding bone to absorb or shrink, thereby causing manual implant failure.
  • the elastic modulus of commercial pure titanium used in clinical dental implants is 110GPa, which is much higher than the elastic modulus of human mandibular cortical bone 10 ⁇ 18GPa and the elastic modulus of cancellous bone 1.5 ⁇ 2.5GPa.
  • the smaller the elastic modulus of the implant material is the closer it is to the elastic modulus of the bone.
  • the smaller the relative displacement caused by the strain difference when the stress is applied the less the tendency of the interface to loosen and avoid. Bone resorption and degradation caused by stress shielding.
  • the elastic modulus of the metal material decreases, the strength and rigidity of the metal material decrease accordingly, so it is difficult to carry the complex stress environment of the oral cavity.
  • the biomechanical compatibility of the dental implant can be solved simply by reducing the elastic modulus of the dental implant.
  • sexual problems there is a suspicion of reluctance.
  • Long-term clinical follow-up studies have shown that the excellent mechanical properties of pure titanium implants can well meet the complex bearing environment requirements of the oral cavity. If the mechanical compatibility problem can be effectively solved, the service life in the body can be far beyond the natural tooth. , significantly improve the long-term success rate of implant dentures.
  • the object of the present invention is to overcome the deficiencies of the prior art, and to provide a bionic dental implant and a preparation method thereof for solving the problem of biomechanical compatibility of dental implants.
  • the invention starts from the principle of bionics, introduces the concept of bionic periodontal film, prepares a low modulus polyurethane coating on the surface of pure titanium, mimics the biomechanical function of the natural periodontal ligament, imparts reasonable physiological mobility to the implant, and occludes the occlusion
  • the force acts as a conduction and buffering force to make the stress distribution on the alveolar bone interface uniform, thus solving the biomechanical compatibility problem of pure titanium implants.
  • the bionic dental implant of the present invention comprises a titanium matrix, a porous titanium dioxide layer impregnated with polyurethane, and a polyurethane layer as a biomimetic periodontal film, wherein the porous titanium dioxide layer impregnated with polyurethane is located between the titanium matrix and the polyurethane layer, respectively It is tightly integrated with the titanium matrix and polyurethane layer.
  • the thickness of the bionic dental implant of the present invention is controlled to be 0.15 mm to 0.25 mm to meet the planting needs of patients of different ages.
  • the preparation method of the bionic dental implant of the invention has the following steps:
  • micron-sized titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting (EBM) to form micron and nanometer pores coexisting and interpenetrating and rich in Ti-OH.
  • EBM electron beam melting
  • a porous titanium dioxide layer of a reactive group the amount of the titanium dioxide powder being limited to a porous titanium dioxide layer capable of forming a thickness of 0.15 mm to 0.3 mm;
  • isophorone diisocyanate from isophorone diisocyanate (IPDI), polyethylene glycol (PEG) or polytetrahydrofuran ether glycol (PTMG) or polycaprolactone (PCL)
  • IPDI isophorone diisocyanate
  • PEG polyethylene glycol
  • PTMG polytetrahydrofuran ether glycol
  • PCL polycaprolactone
  • the polyurethane prepolymer prepared in step 2 is applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a closed container, vacuumed, and maintained at a negative pressure of 0.5 to 1 hour of O.OlMpa ⁇ 0.06 MPa.
  • a polyurethane prepolymer is infiltrated into the pores of the porous titania layer, and a layer of unrolled liquid polyurethane is formed on the surface of the porous titania layer, the polyurethane prepolymer being formed to have a thickness of 0.15 mm to 0.25 mm.
  • the polyurethane layer is limited;
  • the composite having the polyurethane layer obtained in the step 3 is immersed in a chain extender solution having a chain extender concentration of 0.3 g/ml to 0.8 g/ml, and the catalyst stannous octoate is added, and then heated under normal pressure to After incubating at 50 °C ⁇ 55 °C for 2 h ⁇ 3 h, after the end of the heat preservation, the composite body is taken out from the chain extender solution, and air-dried in the air at room temperature to obtain a bionic dental implant. 2% ⁇ 0. 5% ⁇ The amount of the chain agent solution is 0. 2% ⁇ 0. 5%.
  • the chain extender is triethanolamine or trimethylolpropane
  • the chain extender solvent is acetone or N, N-dimethylformamide
  • the particle diameter of the titanium dioxide powder is preferably 50 ⁇ m to 100 ⁇ m.
  • the electron beam melting technology utilizes the heat generated by the high-energy electron beam to form a local high temperature, partially melts the titanium dioxide powder, and fuses the local melting portions to each other by continuous scanning, and joins the linear or planar metal layer to melt layer by layer.
  • the mutually accumulating forms a porous titania layer which forms a coexistence of micro- and nano-scale pores and penetrates between pores and is rich in Ti-OH reactive groups.
  • the process of electron beam melting technology can be referred to the paper "Mechanical properties of rapid fabrication of Ti-6A1-4V by electron beam melting (Lock Red Wave, et al., Aerospace Manufacturing Technology, 2009. 12(06): 18-22)".
  • the polyurethane elastomer Since the outer surface of the bionic dental implant of the present invention is covered with a polyurethane layer, the polyurethane elastomer exhibits a low elastic modulus and a nonlinear viscous property very similar to that of the natural periodontal ligament, and has excellent wear resistance. Corrosion, flexibility and other characteristics, so biomechanical compatibility is better than existing dental implants, and the success rate of planting is improved.
  • the pure titanium matrix of the bionic dental implant of the present invention is bonded to the polyurethane layer by a porous titanium dioxide layer infiltrated with polyurethane, the bonding is tight.
  • the liquid polyurethane prepolymer is prepared by using isophorone diisocyanate, polyethylene glycol, polytetrahydrofuran ether glycol or polycaprolactone as raw materials, thereby forming
  • the polyurethane layer is non-toxic and has no damage to the human body.
  • the method for preparing a bionic dental implant according to the present invention uses an electron beam melting technique to form a porous titanium dioxide layer, thereby not only effectively eliminating the pollution and damage of materials caused by external chemical element impurities, but also enabling the chain extension reaction to proceed more. Sufficient, the monomer utilization is improved, and the polyurethane layer is firmly bonded to the substrate.
  • the preparation method of the bionic dental implant of the present invention uses a vacuum suction method to fully infiltrate the liquid polyurethane prepolymer into the pores of the porous titanium dioxide layer, and forms a plurality of micro-nano-scale anti-reflections on the pure titanium substrate.
  • the kettle is increased, and the reaction efficiency and speed are increased.
  • the chain extension in this manner can control the thickness of the formed polyurethane coating by changing the speed and time of the chain extension reaction to meet the requirements of the dental implant.
  • the preparation method of the bionic dental implant of the present invention uses conventional equipment to facilitate industrial production.
  • Fig. 1 is a cross-sectional structural view showing a bionic dental implant of the present invention, wherein a titanium substrate, a porous titanium dioxide layer impregnated with polyurethane, and a 3-polyurethane layer are used. detailed description
  • the process steps for preparing the bionic dental implant are as follows:
  • the titanium matrix is treated with mixed acid composed of hydrochloric acid and sulfuric acid.
  • the concentration of hydrochloric acid is 36%, the concentration of sulfuric acid is 98%, and 20ml is prepared.
  • Mixed acid, mixed acid, the volume ratio of hydrochloric acid to sulfuric acid is 1: 1
  • Treatment method The polished titanium substrate is placed in a beaker containing the mixed acid, and the beaker is sealed with plastic wrap and placed The titanium substrate was taken out in a water bath at 60 ° C for 30 minutes, and the titanium substrate was placed in an oven and dried at 50 ° C;
  • Titanium dioxide powder is deposited layer by layer on the surface of the acid-treated pure titanium substrate by electron beam melting technology to form a porous titania layer in which micron and nanometer pores coexist and interpenetrating and rich in Ti-OH reactive groups, the titanium dioxide powder
  • the particle diameter is 50 ⁇ m ⁇ 100 ⁇
  • the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, a beam current of 2.0 mA, and a thickness of the porous titanium dioxide layer of 0.15 mm. ;
  • step 2 1.2 g of the polyurethane prepolymer prepared in step 2 was applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, evacuated, and maintained at a negative pressure of 0.06 MPa for 0.5 h to make the polyurethane prepolymer. Infiltrating into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
  • step 4 7.0 g of the chain extender trimethylolpropane (TMP) and 10 ml of N, N-dimethylformamide (DMF) were formulated into a solution and placed in a 50 ml beaker.
  • TMP chain extender trimethylolpropane
  • DMF N, N-dimethylformamide
  • the surface obtained in step 3 was polyurethane.
  • the layer composite is immersed in the above chain extender solution, and 0.05 ml of catalyst stannous octoate is added dropwise, and then the beaker is placed in an oven at 55 ° C for 2 h. After the end of the heat preservation, the composite is removed from the mixture.
  • the chain extender solution is taken out and naturally dried in the air at room temperature to obtain a bionic dental implant composed of a pure titanium substrate 1, a porous titanium dioxide layer 2 infiltrated with polyurethane, and a polyurethane layer 3 as shown in FIG.
  • the thickness of the polyurethane layer is about 0.20 mm.
  • the bionic dental implant prepared in the present example was subjected to a scratch test.
  • the test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
  • the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the biomimetic dental implant biophase prepared in this example. Good compatibility.
  • Example 2
  • the process steps for preparing the bionic dental implant are as follows:
  • the titanium substrate is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
  • the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the acid-treated pure titanium surface by electron beam melting technology to form a porous body.
  • the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
  • the thickness of the porous titanium dioxide layer is 0.20 mm;
  • step 3 The polyurethane prepolymer prepared in step 2 is coated on the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, vacuumed, and maintained at a negative pressure of 0.06 MPa for 1 hour to make the polyurethane prepolymer. Infiltrating into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
  • step 4 6.0 g of the chain extender trimethylolpropane (TMP) and 10 ml of N, N-dimethylformamide (DMF) were formulated into a solution and placed in a 50 ml beaker.
  • TMP chain extender trimethylolpropane
  • DMF N, N-dimethylformamide
  • the surface obtained in step 3 was polyurethane.
  • the layer composite is immersed in the above chain extender solution, and 0.03 ml of catalyst stannous octoate is added dropwise, and then the beaker is placed in an oven at 55 ° C for 3 h. After the end of the heat preservation, the composite is removed from the mixture.
  • the chain extender solution is taken out and naturally dried in the air at room temperature to obtain a bionic dental implant composed of a pure titanium substrate 1, a porous titanium dioxide layer 2 infiltrated with polyurethane, and a polyurethane layer 3 as shown in FIG.
  • the polyurethane layer has a thickness of about 0.15 mm.
  • the bionic dental implant prepared in the present example was subjected to a scratch test. The test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
  • the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the biomimetic dental implant biophase prepared in this example. Good compatibility.
  • the process steps for preparing the bionic dental implant are as follows:
  • the titanium matrix is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
  • the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting technology to form a porous body.
  • the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
  • the thickness of the porous titanium dioxide layer is 0.25 mm;
  • step 3 1.5 g of the polyurethane prepolymer prepared in step 2 was applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, vacuumed, and maintained at a negative pressure of 0.5 MPa for the polyurethane prepolymer. Infiltrating into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
  • step 4 7.5 g of the chain extender trimethylolpropane (TMP) and 10 ml of N, N-dimethylformamide (DMF) were formulated into a solution and placed in a 50 ml beaker.
  • the surface obtained in step 3 was polyurethane.
  • the layer composite is immersed in the above chain extender solution, and 0.05 ml of catalyst stannous octoate is added dropwise, and then the beaker is placed in an oven at 55 ° C for 2.5 h. After the heat preservation, the composite is removed from the mixture.
  • the chain extender solution is taken out and naturally dried in the air at room temperature to obtain a bionic dental implant composed of the titanium substrate 1, the porous titanium dioxide layer 2 infiltrated with the polyurethane, and the polyurethane layer 3 as shown in FIG.
  • the thickness of the layer is approximately 0.25 mm.
  • the bionic dental implant prepared in the present example was subjected to a scratch test. The test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
  • the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the bionic dental implant organism prepared in the present example. Good compatibility.
  • the process steps for preparing the bionic dental implant are as follows:
  • the titanium matrix is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
  • the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting technology to form a porous body.
  • the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
  • the porous titanium dioxide layer has a thickness of 0.15 mm;
  • step 3 1.5 g of the polyurethane prepolymer prepared in step 2 was applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, evacuated, and maintained at a negative pressure of 0.03 MPa for 1 hour to allow the polyurethane prepolymer to penetrate. Advancing into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
  • the bionic dental implant prepared in the present example was subjected to a scratch test. The test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
  • the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the bionic dental implant organism prepared in the present example. Good compatibility.
  • the process steps for preparing the bionic dental implant are as follows:
  • the titanium matrix is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
  • the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting technology to form a porous body.
  • the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
  • the thickness of the porous titania layer is 0.30 mm;
  • step 3 The polyurethane prepolymer prepared in step 2 is applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, vacuumed, and maintained at a negative pressure of 0.03 MPa for 0.5 h to prepolymerize the polyurethane.
  • the body penetrates into the pores of the porous titania layer, and forms a layer of unrolled polyurethane on the surface of the porous titania layer;
  • the bionic dental implant prepared in the present example was subjected to a scratch test.
  • the test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
  • the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the bionic dental implant organism prepared in the present example. Good compatibility.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)

Description

一种仿生牙种植体及其制备方法 技术领域
本发明属于种植牙领域， 特别涉及一种表面覆盖有低模量类牙周膜的纯钛牙 种植体及其制备方法。 背景技术
自 Branemark 提出骨整合理论以来， 种植牙已成功用于修复恒牙缺失， 重建 咀嚼功能。 目前国内外常用的国际知名品牌牙种植系统 （包括英国 Branemark 瑞 士 ITI、 德国 ΙΜΖ、 美国 3i) 以及国产莱顿 BLB等牙种植系统均采用商业纯钛作 为牙种植体， 但临床应用中发现， 即使进口钛种植体， 使用过程中仍存在不同程 度的松动、 脱落、 断裂及周围骨组织炎症等问题， 造成种植失败。 长期临床跟踪 研究发现， 种植牙失败最主要的原因是材料 /组织界面力学性能不相容。众所周知， 人牙与种植牙最关键的解剖结构差异在于牙周膜的有无。天然牙通过牙周膜悬吊在颌骨 内， 当牙齿受力时， 外力通过牙周膜均匀传递和分散至颌骨， 从而引发牙周组织对 外力作用的生理应答； 而骨结合牙种植体与颌骨之间为刚性连接， 二者直接接触， 缺少牙周膜， 当牙种植体弹性模量与颌骨弹性模量不一致时， 种植义齿受到冲击 载荷所产生的冲击能量是通过牙种植体直接传至其周围骨组织， 易导致牙种植体 周围骨组织应力集中， 造成周围骨质吸收或萎缩， 从而使人工种植牙失败。 目前 临床牙种植体所用商业纯钛的弹性模量为 110GPa， 远高于人下颌骨骨皮质的弹性 模量 10~18GPa和松质骨的弹性模量 1.5~2.5GPa。 从医学和生物力学角度看， 种植 体材料的弹性模量越小， 越接近骨的弹性模量， 两者在承受应力时因应变差异造 成的相对位移越小， 可减小界面松动倾向， 避免应力屏蔽造成的骨吸收和退化。 但随着金属材料的弹性模量降低， 其强度和刚性也相应降低， 则难以承载口腔复 杂的应力环境， 如若单纯通过降低牙种植体的弹性模量来解决其植入后的生物力 学相容性问题， 则有舍本逐末之嫌。 长期临床随访研究均表明， 纯钛种植体优异 的机械性能可很好地满足口腔复杂的承载环境要求， 若能有效解决其力学相容性 问题， 则其在体内的服役寿命可远超天然牙， 显著提高种植义齿的远期成功率。 发明内容
本发明的目的在于克服现有技术的不足， 提供一种仿生牙种植体及其制备方法， 以解决牙种植体的生物力学相容性问题。
本发明从仿生学原理出发， 引入仿生牙周膜概念， 在纯钛表面制备低模量聚氨 酯涂层， 以模仿天然牙周膜的生物力学功能， 赋予种植牙合理的生理动度， 并对咬 合力起到传导和缓冲作用， 使牙槽骨界面上应力分布均匀， 从而解决纯钛种植体 的生物力学相容性问题。
本发明所述仿生牙种植体， 由钛基体、 渗透有聚氨酯的多孔二氧化钛层和作为仿 生牙周膜的聚氨酯层构成， 所述渗透有聚氨酯的多孔二氧化钛层位于钛基体和聚氨酯 层之间， 分别与钛基体、 聚氨酯层紧密结合为一体。
由于天然牙通过厚约 0.2mm的牙周膜悬吊在颌骨内， 当牙齿受力时， 外力通 过牙周膜均匀传递和分散至颌骨， 从而引发牙周组织对外力作用的生理应答。 因 而， 本发明所述仿生牙种植体的厚度控制在 0.15mm 〜0.25mm， 以适应不同年龄患 者的种植需求。
本发明所述仿生牙种植体的制备方法， 工艺步骤如下：
①将钛基体进行酸处理， 然后用电子束熔融技术（EBM)在经过酸处理的钛基 体表面逐层沉积微米级二氧化钛粉末， 形成微米和纳米级孔隙共存且孔间贯穿并 富含 Ti-OH 活性基团的多孔二氧化钛层， 所述二氧化钛粉末的量以能形成厚度为 0.15mm~0.3mm的多孔二氧化钛层为限；
②以异佛尔酮二异氰酸酯（ IPDI )、聚乙二醇 (PEG)或聚四氢呋喃醚二醇 (PTMG) 或聚己内酯（PCL) 为原料制备聚氨酯预聚体， 异佛尔酮二异氰酸酯与聚乙二醇或 聚四氢呋喃醚二醇或聚己内酯的摩尔比为 1. 2 : 1〜1 : 1， 将计量好的异佛尔酮二异 氰酸酯、 聚乙二醇或聚四氢呋喃醚二醇或聚己内酯加入装有温度计、 回流冷凝管 和搅拌器的反应容器中， 在氮气保护和搅拌下于常压、 70°C ~80°C下反应 2 h ~3 h， 即得到具有流动性的粘稠状聚氨酯预聚体；
③将步骤②制备的聚氨酯预聚体涂覆于步骤①沉积在钛基体表面的多孔二氧化 钛层上， 然后放入密闭容器中， 抽真空， 保持 O.OlMpa 〜0.06MPa的负压 0.5h~lh， 使聚氨酯预聚体渗入到多孔二氧化钛层的孔中， 并在多孔二氧化钛层的表面形成一 层铺展开的液态聚氨酯层， 所述聚氨酯预聚体的量以能形成厚度为 0.15mm 〜 0.25mm的聚氨酯层为限；
2 ④将步骤③得到的表面有聚氨酯层的复合体浸泡在扩链剂浓度为 0.3g/ml~0.8g/ml 的扩链剂溶液中， 并加入催化剂辛酸亚锡， 然后在常压下加热至 50 °C〜55 °C保温 2 h ~3h， 保温结束后， 将所述复合体从扩链剂溶液中取出， 在室 温下于空气中自然晾干， 即得到仿生牙种植体， 所述扩链剂溶液的量以表面有聚 氨酯层的复合体能完全淹没为限， 所述催化剂辛酸亚锡为扩链剂溶液体积的 0. 2%~0. 5%。
上述方法中， 扩链剂为三乙醇胺或三羟甲基丙烷， 扩链剂溶剂为丙酮或 N， N-二甲基甲酰胺。
上述方法中， 二氧化钛粉末的粒径优选 50μιη ~100μιη。
所述电子束熔融技术是利用高能电子束产生的热量形成局部高温， 使二氧化 钛粉末局部融化， 并通过连续扫描使局部熔融部位相互融合， 连接成线状或面状 金属层， 通过逐层熔融， 相互累加形成形成微米和纳米级孔隙共存且孔间贯穿并 富含 Ti-OH活性基团的多孔二氧化钛层。 电子束熔融技术的工艺可参考论文 "电 子束熔融快速制造 Ti-6A1-4V 的力学性能（ 锁红波等，航天制造技术，2009. 12(06): 18-22 ) "。
本发明具有以下有益效果：
1、 由于本发明所述仿生牙种植体的外表面覆盖有聚氨酯层， 而聚氨酯弹性体 表现出非常类似于天然牙周膜的低弹性模量和非线性粘滞特性， 且具有优异的耐 磨蚀、 柔韧等特性， 因而相对于现有的牙种植体， 生物力学相容性更好， 种植成 功率提高。
2、由于本发明所述仿生牙种植体的纯钛基体与聚氨酯层之间通过渗透有聚氨酯 的多孔二氧化钛层结合， 因而结合紧密。
3、 本发明所述仿生牙种植体的制备方法中， 以异佛尔酮二异氰酸酯、 聚乙二 醇、 聚四氢呋喃醚二醇或聚己内酯为原料制备液态聚氨酯预聚体， 因而所形成的 聚氨酯层无毒性， 对人体无损害。
4、 由于本发明所述仿生牙种植体的制备方法采用电子束熔融技术形成多孔二 氧化钛层， 因而不仅能够有效排除外界化学元素杂质对材料产生的污染和危害， 而 且使得扩链反应能够进行得更充分， 单体利用率提高， 聚氨酯层与基体结合牢固。
5、 由于本发明所述仿生牙种植体的制备方法采用负压抽吸的方式将液态聚氨 酯预聚体充分渗入到多孔二氧化钛层的孔中， 在纯钛基体上形成许多微纳米级的反
3 应釜， 因而提高了反应效率和速度， 而且采用这种方式扩链， 能够通过改变扩链 反应的速度和时间对所形成的聚氨酯涂层的厚度进行控制， 使其达到牙种植体的 要求。
6、 本发明所述仿生牙种植体的制备方法使用常规设备， 便于工业化生产。 附图说明
图 1 是本发明所述仿生牙种植体的的剖面结构示意图， 图中， 1一钛基体、 2 一渗透有聚氨酯的多孔二氧化钛层、 3—聚氨酯层。 具体实施方式
下面通过实施例对本发明所述仿生牙种植体及其制备方法作进一步的详细说 明。 实施例 1
本实施例中， 制备仿生牙种植体的工艺步骤如下：
①钛基体为一颗直径 =4.5mm、 长度 = 12mm的骨螺钉， 将钛基体用盐酸和硫酸 组成的混合酸进行处理，盐酸的质量浓度为 36%，硫酸的质量浓度为 98%，配制 20ml 混合酸， 混合酸中， 盐酸与硫酸的体积比为 1 : 1， 处理方法： 将经过打磨的钛基体 放入盛有所述混合酸的烧杯中， 将所述烧杯用保鲜膜封口并放入 60 °C的水浴中， 恒温 30min后取出钛基体， 并将钛基体放入烘箱在 50°C烘干；
采用电子束熔融技术在经过酸处理的纯钛基体表面逐层沉积二氧化钛粉末， 形成微米和纳米级孔隙共存且孔间贯穿并富含 Ti-OH活性基团的多孔二氧化钛层， 所述二氧化钛粉末的粒径为 50μιη ~100μιη， 所述电子枪真空度为 0.6Mpa， 功率为 5.0kW, 加速电压为 30~60kV， 扫描速度为 800mm/min， 电子束电流为 2.0mA， 多 孔二氧化钛层的厚度为 0.15mm;
②以异佛尔酮二异氰酸酯 （IPDI)、 聚四氢呋喃醚二醇 2000 ( PTMG-2000 ) 为 原料制备聚氨酯预聚体， 将 13g异佛尔酮二异氰酸酯 （IPDI) 与 50g聚四氢呋喃 醚二醇 2000 ( PTMG-2000)加入装有温度计、 回流冷凝管和搅拌器的三口烧瓶中， 在氮气保护和搅拌下于常压、 70 °C下反应 2h， 得到具有流动性的粘稠状聚氨酯预
4 聚体 （IPDI与 PTMG-2000的摩尔比 = 1.2: 1 ) ;
③将步骤②制备的聚氨酯预聚体 1.2g涂覆于步骤①沉积在钛基体表面的多孔二 氧化钛层上， 然后放入真空泵， 抽真空， 保持 0.06MPa的负压 0.5h， 使聚氨酯预聚 体渗入到多孔二氧化钛层的孔中， 并在多孔二氧化钛层的表面形成一层铺展开的聚 氨酯层；
④将 7.0g的扩链剂三羟甲基丙烷（TMP)和 10ml的 N， N-二甲基甲酰胺（DMF ) 配制成溶液并盛在 50ml 的烧杯中， 将步骤③得到的表面有聚氨酯层的复合体浸泡 在上述扩链剂溶液中， 并滴入 0.05ml催化剂辛酸亚锡， 然后将所述烧杯放入 55 °C 的烘箱中保温 2 h， 保温结束后， 将所述复合体从扩链剂溶液中取出， 在室温下于 空气中自然晾干， 即可得到图 1所示的依次由纯钛基体 1、 渗透有聚氨酯的多孔二 氧化钛层 2和聚氨酯层 3构成的仿生牙种植体， 聚氨酯层的厚度约为 0.20mm。
将本实施例所制备的仿生牙种植体进行划痕试验， 试验结果显示， 当聚氨酯 层内产生微裂纹时， 渗透有聚氨酯的多孔二氧化钛层与聚氨酯层之间、 渗透有聚氨 酯的多孔二氧化钛层与钛基体之间均未产生脱离现象， 表明它们之间结合紧密。 将 本实施例所制备的仿生牙种植体浸泡在 37°C过饱和磷酸钙溶液中 24h， 在聚氨酯 层表面有一定量的类 HA晶体长出，表明本实施例所制备的仿生牙种植体生物相容 性良好。 实施例 2
本实施例中， 制备仿生牙种植体的工艺步骤如下：
①钛基体为一颗直径 =4.5mm、 长度 = 12mm的骨螺钉， 钛基体的酸处理与实施 例 1相同； 采用电子束熔融技术在经过酸处理的纯钛表面逐层沉积二氧化钛粉末， 形成多孔二氧化钛层， 所述二氧化钛粉末的粒径为 50μιη ~100μιη， 所述电子枪真空 度为 0.6Mpa， 功率为 5.0kW， 加速电压为 30~60kV， 扫描速度为 800mm/min， 电 子束电流为 2.0mA， 多孔二氧化钛层的厚度为 0.20mm;
②以异佛尔酮二异氰酸酯 （IPDI)、 聚己内酯 2000 ( PCL-2000) 为原料制备聚 氨酯预聚体，将 10g异佛尔酮二异氰酸酯（IPDI)与 50g聚己内酯 2000 ( PCL-2000) 加入装有温度计、 回流冷凝管和搅拌器的三口烧瓶中， 在氮气保护和搅拌下于常 压、 75 °C下反应 3h， 得到具有流动性的粘稠状聚氨酯预聚体 （IPDI与 PCL -2000 的摩尔比 = 1 : 1 );
③将步骤②制备的聚氨酯预聚体 l .Og涂覆于步骤①沉积在钛基体表面的多孔二 氧化钛层上， 然后放入真空泵， 抽真空， 保持 0.06MPa的负压 lh， 使聚氨酯预聚 体渗入到多孔二氧化钛层的孔中， 并在多孔二氧化钛层的表面形成一层铺展开的聚 氨酯层；
④将 6.0g的扩链剂三羟甲基丙烷（TMP)和 10ml的 N， N-二甲基甲酰胺（DMF ) 配制成溶液并盛在 50ml 的烧杯中， 将步骤③得到的表面有聚氨酯层的复合体浸泡 在上述扩链剂溶液中， 并滴入 0.03ml催化剂辛酸亚锡， 然后将所述烧杯放入 55 °C 的烘箱中保温 3 h， 保温结束后， 将所述复合体从扩链剂溶液中取出， 在室温下于 空气中自然晾干， 即可得到图 1所示依次由纯钛基体 1、 渗透有聚氨酯的多孔二氧 化钛层 2和聚氨酯层 3构成的仿生牙种植体， 聚氨酯层的厚度约为 0.15mm。
将本实施例所制备的仿生牙种植体进行划痕试验， 试验结果显示， 当聚氨酯 层内产生微裂纹时， 渗透有聚氨酯的多孔二氧化钛层与聚氨酯层之间、 渗透有聚氨 酯的多孔二氧化钛层与钛基体之间均未产生脱离现象， 表明它们之间结合紧密。 将 本实施例所制备的仿生牙种植体浸泡在 37°C过饱和磷酸钙溶液中 24h， 在聚氨酯 层表面有一定量的类 HA晶体长出，表明本实施例所制备的仿生牙种植体生物相容 性良好。 实施例 3
本实施例中， 制备仿生牙种植体的工艺步骤如下：
①钛基体为一颗直径 =4.5mm、 长度 = 12mm的骨螺钉， 钛基体的酸处理与实施 例 1 相同； 采用电子束熔融技术在经过酸处理的钛基体表面逐层沉积二氧化钛粉 末， 形成多孔二氧化钛层， 所述二氧化钛粉末的粒径为 50μιη ~100μιη， 所述电子枪 真空度为 0.6Mpa， 功率为 5.0kW， 加速电压为 30~60kV， 扫描速度为 800mm/min， 电子束电流为 2.0mA， 多孔二氧化钛层的厚度为 0.25mm;
②以异佛尔酮二异氰酸酯 （IPDI)、 聚四氢呋喃醚二醇 1000 ( PTMG-1000 ) 为 原料制备聚氨酯预聚体， 将 12g异佛尔酮二异氰酸酯 （IPDI) 与 25g聚四氢呋喃 醚二醇 1000 ( PTMG-1000)加入装有温度计、 回流冷凝管和搅拌器的三口烧瓶中， 在氮气保护和搅拌下于常压、 80 °C下反应 2.5h， 得到具有流动性的粘稠状聚氨酯
6 预聚体 （IPDI与 PTMG-1000的摩尔比 = 1.1 : 1 );
③将步骤②制备的聚氨酯预聚体 1.5g涂覆于步骤①沉积在钛基体表面的多孔二 氧化钛层上， 然后放入真空泵， 抽真空， 保持 O.OlMPa的负压 lh， 使聚氨酯预聚 体渗入到多孔二氧化钛层的孔中， 并在多孔二氧化钛层的表面形成一层铺展开的聚 氨酯层；
④将 7.5g的扩链剂三羟甲基丙烷（TMP)和 10ml的 N， N-二甲基甲酰胺（DMF ) 配制成溶液并盛在 50ml 的烧杯中， 将步骤③得到的表面有聚氨酯层的复合体浸泡 在上述扩链剂溶液中， 并滴入 0.05ml催化剂辛酸亚锡， 然后将所述烧杯放入 55 °C 的烘箱中保温 2.5 h， 保温结束后， 将所述复合体从扩链剂溶液中取出， 在室温下 于空气中自然晾干， 即可得到图 1所示依次由钛基体 1、 渗透有聚氨酯的多孔二氧 化钛层 2和聚氨酯层 3构成的仿生牙种植体， 聚氨酯层的厚度约为 0.25mm。
将本实施例所制备的仿生牙种植体进行划痕试验， 试验结果显示， 当聚氨酯 层内产生微裂纹时， 渗透有聚氨酯的多孔二氧化钛层与聚氨酯层之间、 渗透有聚氨 酯的多孔二氧化钛层与钛基体之间均未产生脱离现象， 表明它们之间结合紧密。 将 本实施例所制备的仿生牙种植体浸泡在 37 °C过饱和磷酸钙溶液中 24 h， 在聚氨 酯层表面有一定量的类 HA晶体长出，表明本实施例所制备的仿生牙种植体生物相 容性良好。 实施例 4
本实施例中， 制备仿生牙种植体的工艺步骤如下：
①钛基体为一颗直径 =4.5mm、 长度 = 12mm的骨螺钉， 钛基体的酸处理与实施 例 1 相同； 采用电子束熔融技术在经过酸处理的钛基体表面逐层沉积二氧化钛粉 末， 形成多孔二氧化钛层， 所述二氧化钛粉末的粒径为 50μιη ~100μιη， 所述电子枪 真空度为 0.6Mpa， 功率为 5.0kW， 加速电压为 30~60kV， 扫描速度为 800mm/min， 电子束电流为 2.0mA， 多孔二氧化钛层的厚度为 0.15mm;
②以异佛尔酮二异氰酸酯 （IPDI)、 聚乙二醇 1000 ( PEG- 1000 ) 为原料制备液 态聚氨酯预聚体， 将 17g 异佛尔酮二异氰酸酯 （IPDI ) 与 25g 聚乙二醇 1000
( PEG- 1000 ) 加入装有温度计、 回流冷凝管和搅拌器的三口烧瓶中， 在氮气保护 和搅拌下于常压、 70 °C下反应 3h， 得到具有流动性的粘稠状聚氨酯预聚体 （IPDI 与 PEG- 1000的摩尔比 = 1.2: 1 ) ;
③将步骤②制备的聚氨酯预聚体 1.5g涂覆于步骤①沉积在钛基体表面的多孔二 氧化钛层上， 然后放入真空泵， 抽真空， 保持 0.03MPa的负压 lh， 使聚氨酯预聚 体渗入到多孔二氧化钛层的孔中， 并在多孔二氧化钛层的表面形成一层铺展开的聚 氨酯层；
④将 4.5g扩链剂三乙醇胺 （TEOA) 用 10ml丙酮稀释后盛在 50ml的烧杯中， 将步骤③得到的表面有聚氨酯层的复合体浸泡在上述扩链剂溶液中， 并滴入 0.06ml 催化剂辛酸亚锡， 然后将所述烧杯放入 50°C的烘箱中保温 2.5 h， 保温结束后， 将 所述复合体从扩链剂溶液中取出， 在室温下于空气中自然晾干， 即可得到图 1 所 示依次由纯钛基体 1、 渗透有聚氨酯的多孔二氧化钛层 2和聚氨酯层 3构成的结构的 仿生牙种植体， 聚氨酯层的厚度约为 0.25mm。
将本实施例所制备的仿生牙种植体进行划痕试验， 试验结果显示， 当聚氨酯 层内产生微裂纹时， 渗透有聚氨酯的多孔二氧化钛层与聚氨酯层之间、 渗透有聚氨 酯的多孔二氧化钛层与钛基体之间均未产生脱离现象， 表明它们之间结合紧密。 将 本实施例所制备的仿生牙种植体浸泡在 37 °C过饱和磷酸钙溶液中 24 h， 在聚氨酯 层表面有一定量的类 HA晶体长出，表明本实施例所制备的仿生牙种植体生物相容 性良好。 实施例 5
本实施例中， 制备仿生牙种植体的工艺步骤如下：
①钛基体为一颗直径 =4.5mm、 长度 = 12mm的骨螺钉， 钛基体的酸处理与实施 例 1 相同； 采用电子束熔融技术在经过酸处理的钛基体表面逐层沉积二氧化钛粉 末， 形成多孔二氧化钛层， 所述二氧化钛粉末的粒径为 50μιη ~100μιη， 所述电子枪 真空度为 0.6Mpa， 功率为 5.0kW， 加速电压为 30~60kV， 扫描速度为 800mm/min， 电子束电流为 2.0mA， 多孔二氧化钛层的厚度为 0.30mm;
②以异佛尔酮二异氰酸酯 （IPDI)、 聚乙二醇 2000 ( PEG-2000 ) 为原料制备液 态聚氨酯预聚体， 将 15g 异佛尔酮二异氰酸酯 （IPDI ) 与 50g 聚乙二醇 2000
( PEG-2000 ) 加入装有温度计、 回流冷凝管和搅拌器的三口烧瓶中， 在氮气保护 和搅拌下于常压、 70 °C下反应 2.5h，得到具有流动性的粘稠状聚氨酯预聚体（IPDI
8 与 PEG-2000的摩尔比 = 1.1 : 1 ) ;
③将步骤②制备的聚氨酯预聚体 l . lg涂覆于步骤①沉积在钛基体表面的多孔二 氧化钛层上， 然后放入真空泵， 抽真空， 保持 0.03MPa的负压 0.5h， 使聚氨酯预聚 体渗入到多孔二氧化钛层的孔中， 并在多孔二氧化钛层的表面形成一层铺展开的聚 氨酯层；
④将 3.4g扩链剂三乙醇胺 （TEOA) 用 10ml丙酮稀释后盛在 50ml的烧杯中， 将步骤③得到的表面有聚氨酯层的复合体浸泡在上述扩链剂溶液中， 并滴入 0.04ml 催化剂辛酸亚锡， 然后将所述烧杯放入 50°C的烘箱中保温 3 h， 保温结束后， 将所 述复合体从扩链剂溶液中取出， 在室温下于空气中自然晾干， 即可得到图 1 所示 依次由纯钛基体 1、 渗透有聚氨酯的多孔二氧化钛层 2和聚氨酯层 3构成的仿生牙种 植体， 聚氨酯层的厚度约为 0.17mm。
将本实施例所制备的仿生牙种植体进行划痕试验， 试验结果显示， 当聚氨酯 层内产生微裂纹时， 渗透有聚氨酯的多孔二氧化钛层与聚氨酯层之间、 渗透有聚氨 酯的多孔二氧化钛层与钛基体之间均未产生脱离现象， 表明它们之间结合紧密。 将 本实施例所制备的仿生牙种植体浸泡在 37°C过饱和磷酸钙溶液中 24 h， 在聚氨酯 层表面有一定量的类 HA晶体长出，表明本实施例所制备的仿生牙种植体生物相容 性良好。
9

Claims

权利要求书
1、 一种仿生牙种植体， 其特征在于由钛基体 （1 )、 渗透有聚氨酯的多孔 二氧化钛层 （2 ) 和作为仿生牙周膜的聚氨酯层 （3 ) 构成， 所述渗透有聚氨酯 的多孔二氧化钛层 （2)位于钛基体 （1 ) 和聚氨酯层 （3 )之间， 分别与钛基体 ( 1 )、 聚氨酯层 （3 ) 紧密结合为一体。
2、 根据权利要求 1所述仿生牙种植体， 其特征在于渗透有聚氨酯的多孔 二氧化钛层 （2) 的厚度为 0.15~0.3mm， 聚氨酯层 （3 ) 的厚度为 0.15mm 〜 0.25mm。
3、 一种仿生牙种植体的制备方法， 其特征在于工艺步骤如下：
①将钛基体进行酸处理，然后用电子束熔融技术在经过酸处理的钛基体 表面逐层沉积微米级二氧化钛粉末， 形成微米和纳米级孔隙共存且孔间贯 穿并富含 Ti-OH活性基团的多孔二氧化钛层， 所述二氧化钛粉末的量以能形 成厚度为 0. 15mm~0.3mm的多孔二氧化钛层为限；
②以异佛尔酮二异氰酸酯、聚乙二醇或聚四氢呋喃醚二醇或聚己内酯为 原料制备聚氨酯预聚体， 异佛尔酮二异氰酸酯与聚乙二醇或聚四氢呋喃醚 二醇或聚己内酯的摩尔比为 1. 2 : 1〜1 : 1，将计量好的异佛尔酮二异氰酸酯、 聚乙二醇或聚四氢呋喃醚二醇或聚己内酯加入装有温度计、 回流冷凝管和 搅拌器的反应容器中，在氮气保护和搅拌下于常压、 70°C ~80°C下反应 2 h ~3 h， 即得到具有流动性的粘稠状聚氨酯预聚体；
③将步骤②制备的聚氨酯预聚体涂覆于步骤①沉积在钛基体表面的多孔 二氧化钛层上， 然后放入密闭容器中， 抽真空， 保持 O.OlMpa 〜0.06MPa 的负压 0.5h~lh， 使聚氨酯预聚体渗入到多孔二氧化钛层的孔中， 并在多孔 二氧化钛层的表面形成一层铺展开的聚氨酯层， 所述聚氨酯预聚体的量以能 形成厚度为 0.15mm 〜0.25mm的聚氨酯层为限；
④将步骤③得到的表面有聚氨酯层的复合体浸泡在扩链剂浓度为 0.3g/ml~0.8g/ml 的扩链剂溶液中， 并加入催化剂辛酸亚锡， 然后在常压下 加热至 50°C〜55 °C保温 2 h ~3h， 保温结束后， 将所述复合体从扩链剂溶液 中取出， 在室温下于空气中自然晾干， 即得到仿生牙种植体， 所述扩链剂 溶液的量以表面有聚氨酯层的复合体能完全淹没为限， 所述催化剂辛酸亚
10 锡为扩链剂溶液体积的 0.2%~0.5%。
4、根据权利要求 3所述仿生牙种植体的制备方法， 其特征在于扩链剂为 三乙醇胺或三羟甲基丙烷， 扩链剂的溶剂为丙酮或 N， N-二甲基甲酰胺。
5、 根据权利要求 3或 4所述仿生牙种植体的制备方法， 其特征在于所 述二氧化钛粉末的粒径为 50μιη ~100μηι。
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