Summary of the invention
At above problem, the objective of the invention is to prepare a kind of artificial blood vessel with favorable elasticity, reach the requirement of clinical use.Technical scheme of the present invention to achieve these goals is:
A kind of polyethylene terephthalate and polyurethane composite artificial blood vessel, the artificial blood vessel is meant the tube with microcellular structure that is formed by the electrostatic spinning apparatus preparation by polyethylene terephthalate and polyurethane mixed solution, wherein, artificial blood vessel's component is
Polyethylene terephthalate 60-95 part
Polyurethane 5-40 part
Wherein, described polyurethane be CorethaneTM,
80A,
90A, Chronoflex AR, Chronoflex CL,
Elast Eon, Cardiomat or Avcothane.
Described artificial blood vessel's internal diameter is 1mm~30mm;
Described artificial blood vessel's wall thickness is 100 μ m~1.5mm;
The preparation process of polyethylene terephthalate and polyurethane composite artificial blood vessel is as follows:
The preparation of a solution:
Polyethylene terephthalate 60-95 part and polyurethane 5-40 part are dissolved in the hexafluoroisopropanol solvent jointly, are 5~12% spinning solution through being stirred well to fully dissolving, making mass fraction;
B artificial blood vessel's preparation:
To be encased in the electrostatic spinning apparatus that has agitator through the spinning solution of a preparation, adopt drum die as receiving device, spinning solution is stirred in the process that device stirs through the speed ejection of spinning-nozzle with 0.1-2ml/h, entering voltage is 15-25Kv, distance is the high-tension electricity place of 50-300mm, forms the composite fibre of polyethylene terephthalate and polyurethane, is collected on the drum die of doing rotation and straight reciprocating motion, formation has artificial blood vessel's structure of micropore
Wherein, described composite fibre diameter is 50nm~100 μ m;
The rotating speed of described agitator is 10~50 commentaries on classics/min;
The rotary speed of described drum die is 10~100 commentaries on classics/min;
The speed of the straight reciprocating motion of described drum die is 100mm/min~500mm/min.
The axis normal of described drum die is in the nozzle of electrospinning device.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 10~30 ℃ the distilled water and soak 3~6h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 40~60 ℃ of vacuum conditions and carries out drying, the artificial blood vessel who promptly makes polyethylene terephthalate and polyurethane behind dry 6~10h.
Owing to adopt above technical scheme, the polyethylene terephthalate and the polyurethane composite artificial blood vessel Main Ingredients and Appearance of the present invention's preparation are polyethylene terephthalate and polyurethane, wherein polyethylene terephthalate materials is a kind of material with fine brute force and fine wearability, and polyurethane material is a kind of material with favorable elasticity, two kinds of material mixing with different mechanical characteristics are prepared into the shortcoming that product can remedy the homogenous material product together, therefore the polyethylene terephthalate and the polyurethane artificial blood vessel of the present invention's preparation have better elastic and mechanical property, the requirement of clinical use can be satisfied, the difficult problem of the clinical middle terylene artificial blood vessel poor flexibility of using can be overcome.In artificial blood vessel's course of processing, use agitator spinning solution to be stirred on one side, Yi Bian carry out spinning, realized the synchronous of two kinds of material mixing of polyethylene terephthalate and polyurethane and spinning, keep two kinds of material mixing even, prevent layering.The speed controlling of agitator both can play at 10~50 commentaries on classics/min that polymer mixed was acted on uniformly, also can not influence spinning speed simultaneously.Both contained polyethylene terephthalate materials in the every nanofiber of preparation, and also contained simultaneously and have fine elastic polyurethane with fine intensity.How much polyurethane content has determined elasticity of blood vessels among the artificial blood vessel.Polyurethane content is high more in the blood vessel, and elasticity of blood vessels is good more.But along with the increase of polyurethane content, the hot strength of blood vessel descends, so the content of polyurethane is not suitable for surpassing 40% among the artificial blood vessel.Mainly with replacing the natural blood vessel that damages in the human body clinically, artificial blood vessel's internal diameter must be consistent with the diameter of human body natural's blood vessel the artificial blood vessel of preparation.The diameter of main dependence swing roller is controlled the internal diameter of blood vessel among the present invention, reaches the artificial blood vessel of preparation different inner diameters by the drum die of changing different-diameter.The thickness of blood vessel wall is by deciding process time.In the course of processing, the constant airspeed of spinning, the spinning time is long more, and the polymer that cylinder surface receives is many more, and artificial blood vessel's wall thickness is also thick more.The wall thickness of human body real blood vessels is generally 100 μ m~1.5mm, by control spinning speed and the spinning time acquisition thickness similar to the human vas wall thickness.The drum die of rotation and straight reciprocating motion is the receiving device of artificial blood vessel, has directly determined the shape of blood vessel and the uniformity coefficient of wall thickness.The rotating speed of cylinder is that the speed of 10~100 commentaries on classics/min and straight reciprocating motion is that 100mm/min~500mm/min can guarantee to obtain to have the uniform artificial blood vessel of wall thickness.Because the present invention adopts the polyester material of clinical use and has the polyurethane material of good biocompatibility and anticoagulant property, therefore the composite artificial blood vessel of preparation has good biocompatibility, anticoagulant property, cell adhesion, elasticity and compliance can satisfy the requirement of clinical use.
Polyethylene terephthalate of the present invention and polyurethane artificial blood vessel have big, the good biocompatibility of powerful height, elasticity and compliance, and anticoagulant property is strong, and cell adhesion is big, can satisfy the requirement of the clinical use of large and small bore artificial blood vessel.The preparation that preparation technology of the present invention is simple, practical, the various different mechanical properties of adaptation require artificial blood vessels.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
A kind of polyethylene terephthalate and polyurethane composite artificial blood vessel, the artificial blood vessel is meant the tube with microcellular structure that is formed by the electrostatic spinning apparatus preparation by polyethylene terephthalate and polyurethane mixed solution, wherein, artificial blood vessel's component is
Polyethylene terephthalate 60-95 part
Polyurethane 5-40 part
Wherein, described polyurethane be CorethaneTM,
80A,
90A, Chronoflex AR, Chronoflex CL,
Elast Eon, Cardiomat or Avcothane.
The preparation process of polyethylene terephthalate and polyurethane composite artificial blood vessel is as follows:
The preparation of a solution:
Polyethylene terephthalate 60-95 part and polyurethane 5-40 part are dissolved in the hexafluoroisopropanol solvent jointly, are 5~12% spinning solution 4 through being stirred well to fully dissolving, making mass fraction;
B artificial blood vessel's preparation:
To be encased in the solution tank 2 of the electrostatic spinning apparatus that has agitator 3 through the spinning solution 4 of a preparation, agitator 3 places solution tank 2, agitator 3 stirs spinning solution 4 with the rotating speed of 10~50 commentaries on classics/min, make polyethylene terephthalate and polyurethane uniform mixing in the spinning solution 4, artificial blood vessel's structure formation adopts drum die 7 as receiving device, drum die 7 is positioned at the below of electrostatic spinning apparatus nozzle 5, its axis normal is in the nozzle 5 of electrostatic spinning apparatus, rotary speed 10~100 commentaries on classics/min of drum die 7, the straight reciprocating motion speed of drum die 7 is 100mm/min~500mm/min, spinning solution 4 is released through nozzle 5 by micro-injection pump 1 speed with 0.1-2ml/h from solution tank 2 in the process that agitator 3 stirs, entering voltage is 15-25Kv, distance is the high-tension electricity place 6 of 50-300mm, form the composite fibre of polyethylene terephthalate and polyurethane, composite fibre is collected on the drum die 7 of doing rotation and straight reciprocating motion, the composite fibre diameter of collecting is 50nm~100 μ m, forming internal diameter is that 1mm~30mm and wall thickness are 100 μ m~1.5mm artificial blood vessel structure, the internal diameter of artificial blood vessel's structure is directly decided by the diameter of drum die, the wall thickness of artificial blood vessel's structure is relevant with the time, under the constant precondition of spinning speed, the time of drum die collection fiber is long more, and the wall thickness that obtains artificial blood vessel's structure is thick more.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 10~30 ℃ the distilled water and soak 3~6h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 40~60 ℃ of vacuum conditions and carries out drying, the artificial blood vessel who promptly makes polyethylene terephthalate and polyurethane behind dry 6~10h.。
Preparation method below in conjunction with above-mentioned polyethylene terephthalate and polyurethane composite artificial blood vessel is further elaborated with regard to specific embodiment.
Specific embodiment
Embodiment one
A takes by weighing 4.75g polyethylene terephthalate and 0.25g polyurethane (CorethaneTM) on the precise electronic balance, fully be dissolved in the 95g hexafluoroisopropanol, and acquisition concentration is 5% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 95/5.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 10 commentaries on classics/min, select for use diameter be the drum die of 1mm as gathering-device, the rotary speed of setting drum die is 10 commentaries on classics/min, the speed of straight reciprocating motion is 100mm/min.It is 15KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 0.1ml/h, electric field distance is in the high voltage electric field of 50mm, it is the composite fibre 6h of 100 μ m that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 1mm, and wall thickness is artificial blood vessel's structure of 100 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 10 ℃ the distilled water and soak 3h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 40 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 6h.
Embodiment two
A on the precise electronic balance, take by weighing 8g polyethylene terephthalate and 2g polyurethane (
80A), fully be dissolved in the 90g hexafluoroisopropanol, acquisition concentration is 10% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 80/20.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 50 commentaries on classics/min, selecting diameter for use is that the drum die of 30mm is as gathering-device, the rotary speed of setting drum die is 100 commentaries on classics/min, and the speed of straight reciprocating motion is 500mm/min.It is 25KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 0.1ml/h, electric field distance is in the high voltage electric field of 300mm, it is the composite fibre 6h of 50nm that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 30mm, and wall thickness is artificial blood vessel's structure of 100 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 30 ℃ the distilled water and soak 6h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 60 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 10h.
Embodiment three
A on the precise electronic balance, take by weighing 8g polyethylene terephthalate and 2g polyurethane (
90A), fully be dissolved in the 90g hexafluoroisopropanol, acquisition concentration is 10% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 80/20.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 30 commentaries on classics/min, selecting diameter for use is that the drum die of 10mm is as gathering-device, the rotary speed of setting drum die is 50 commentaries on classics/min, and the speed of straight reciprocating motion is 300mm/min.It is 20KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 0.5ml/h, electric field distance is in the high voltage electric field of 200mm, it is the composite fibre 10h of 500nm that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 10mm, and wall thickness is artificial blood vessel's structure of 600 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 20 ℃ the distilled water and soak 4h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 50 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 8h.
Embodiment four
A takes by weighing 7.2g polyethylene terephthalate and 4.8g polyurethane (Chronoflex AR) on the precise electronic balance, fully be dissolved in the 88g hexafluoroisopropanol, and acquisition concentration is 12% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 60/40.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 30 commentaries on classics/min, select for use diameter be the drum die of 6mm as gathering-device, the rotary speed of setting drum die is 50 commentaries on classics/min, the speed of straight reciprocating motion is 100mm/min.It is 20KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 0.5ml/h, electric field distance is in the high voltage electric field of 200mm, it is the composite fibre 24h of 500 μ m that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 6mm, and wall thickness is artificial blood vessel's structure of 1.5mm.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 30 ℃ the distilled water and soak 6h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 50 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 8h.
Embodiment five
A takes by weighing 4.75g polyethylene terephthalate and 0.25g polyurethane (Chronoflex CL) on the precise electronic balance, fully be dissolved in the 95g hexafluoroisopropanol, and acquisition concentration is 5% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 95/5.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 20 commentaries on classics/min, selecting diameter for use is that the drum die of 10mm is as gathering-device, the rotary speed of setting drum die is 20 commentaries on classics/min, and the speed of straight reciprocating motion is 300mm/min.It is 25KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 1ml/h, electric field distance is in the high voltage electric field of 150mm, it is the composite fibre 16h of 400nm that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 10mm, and wall thickness is artificial blood vessel's structure of 900 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 20 ℃ the distilled water and soak 3h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 40 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 10h.
Embodiment six
A on the precise electronic balance, take by weighing 8g polyethylene terephthalate and 2g polyurethane (
), fully being dissolved in the 90g hexafluoroisopropanol, acquisition concentration is 10% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 80/20.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 10 commentaries on classics/min, selecting diameter for use is that the drum die of 20mm is as gathering-device, the rotary speed of setting drum die is 10 commentaries on classics/min, and the speed of straight reciprocating motion is 100mm/min.It is 20KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 1ml/h, electric field distance is in the high voltage electric field of 150mm, it is the composite fibre 10h of 50 μ m that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 20mm, and wall thickness is artificial blood vessel's structure of 300 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 10 ℃ the distilled water and soak 6h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 50 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 10h.
Embodiment seven
A takes by weighing 4.75g polyethylene terephthalate and 0.25g polyurethane (Elast Eon) on the precise electronic balance, fully be dissolved in the 95g hexafluoroisopropanol, and acquisition concentration is 5% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 95/5.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 10 commentaries on classics/min, select for use diameter be the drum die of 1mm as gathering-device, the rotary speed of setting drum die is 10 commentaries on classics/min, the speed of straight reciprocating motion is 100mm/min.It is 15KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 0.1ml/h, electric field distance is in the high voltage electric field of 50mm, it is the composite fibre 6h of 100 μ m that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 1mm, and wall thickness is artificial blood vessel's structure of 100 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 10 ℃ the distilled water and soak 3h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 40 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 6h.
Embodiment eight
A takes by weighing 7.2g polyethylene terephthalate and 4.8g polyurethane (Cardiomat) on the precise electronic balance, fully be dissolved in the 88g hexafluoroisopropanol, and acquisition concentration is 12% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 60/40.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 20 commentaries on classics/min, select for use diameter be the drum die of 6mm as gathering-device, the rotary speed of setting drum die is 20 commentaries on classics/min, the speed of straight reciprocating motion is 200mm/min.It is 20KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 0.5ml/h, electric field distance is in the high voltage electric field of 150mm, it is the composite fibre 8h of 300nm that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 6mm, and wall thickness is artificial blood vessel's structure of 150 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 30 ℃ the distilled water and soak 4h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 50 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 10h.
Embodiment nine
A takes by weighing 4.75g polyethylene terephthalate and 0.25g polyurethane (Avcothane) on the precise electronic balance, fully be dissolved in the 95g hexafluoroisopropanol, and acquisition concentration is 5% spinning solution.Wherein the mass ratio between polyethylene terephthalate and the polyurethane is 95/5.
The spinning solution of b preparation joins electrostatic spinning with in the solution tank, agitator stirs spinning solution with the rotating speed of 10 commentaries on classics/min, selecting diameter for use is that the drum die of 10mm is as gathering-device, the rotary speed of setting drum die is 10 commentaries on classics/min, and the speed of straight reciprocating motion is 100mm/min.It is 20KV that micro-injection pump is pushed into voltage with the spinning solution that stirs through nozzle with the fltting speed of 0.8ml/h, electric field distance is in the high voltage electric field of 300mm, it is the composite fibre 8h of 250nm that drum die receives the diameter that comes out through high voltage electric field continuously, the formation internal diameter is 10mm, and wall thickness is artificial blood vessel's structure of 250 μ m.
C takes off the artificial blood vessel's structure after drum die is collected, be placed in 30 ℃ the distilled water and soak 6h, use fresh distilled water to replace original soak every 1h, artificial blood vessel after the immersion puts under 60 ℃ of vacuum conditions and carries out drying, promptly makes the artificial blood vessel of polyethylene terephthalate and polyurethane behind the dry 8h.