CN113444342B - Material for manufacturing catheter pump motor and preparation method thereof - Google Patents
Material for manufacturing catheter pump motor and preparation method thereof Download PDFInfo
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Abstract
The invention provides a material for manufacturing a catheter pump motor and a preparation method thereof, and relates to the technical field of medical high polymer materials. The material consists of A, B bi-components, wherein the A, B component comprises the following raw materials in parts by weight: the component A comprises: 80-100 parts of bisphenol A epoxy resin E5180, 5-5 parts of modified nano SiO21 and 2-7 parts of epoxypropane benzyl ether; and the component B comprises: 10-20 parts of polyamide curing agent, 1-4 parts of T31 curing agent, 8-16 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent, 0.5-5 parts of organosilicon coupling agent ND-421-7 parts, silicate filler, 3-9 parts of heat-conducting insulating filler and 9-15 parts of titanium dioxide. The material prepared by the invention has the advantages of short curing time, corrosion resistance, high temperature resistance, heat dissipation, good insulativity and the like.
Description
Technical Field
The invention relates to the technical field of medical polymer materials, in particular to a material for manufacturing a catheter pump motor and a preparation method thereof.
Background
The catheter pump is an intravascular micro-shaft blood pump for supporting the blood circulation system of a patient, can be subcutaneously inserted into the left ventricle through the femoral artery or the axillary artery, and after the proper positioning, the blood in the left ventricle is conveyed to the blood outlet of the catheter pump positioned in the ascending aorta through the blood inflow port of the catheter pump to assist the blood circulation.
The prior art catheter pump includes a pigtail, a blood flow inlet, a cannula, a blood flow outlet, an axial impeller, a motor, a catheter, etc., as shown in fig. 1. The motor comprises a bearing, a rotating shaft, a stator, a coil winding, a rotor, fluid flowing on the surface of the rotor, an external shell and an inner cavity insulating layer. In the specific working process, the motor drives the axial flow impeller to rotate, blood is pumped to the aorta from the left ventricle, the blood circulation of a patient is assisted, fluid moves to the blood outflow port along the gap between the surface of the rotor and the stator under external pressure and then enters the aorta, and the phenomenon that the blood enters the motor to form thrombus and reduce the service life of the motor is avoided. The fluid is typically saline or a glucose solution.
The motor outer shell and the inner cavity insulating layer are made of epoxy resin materials, all the components except the rotor are coated and molded together through a vacuum injection molding technology to form a motor whole, and the structure of the motor is shown in figure 2. The epoxy resin is a high molecular polymer with a molecular formula of (C)11H12O3)nThe epoxy resin is a polymer containing more than two epoxy groups in the molecule, is a polycondensation product of epoxy chloropropane and bisphenol A or polyhydric alcohol, is a thermosetting resin, and has the advantages of strong adhesive force, excellent dielectric property, good chemical corrosion resistance and the like.
In the current research, when the epoxy resin is used as a material of a motor shell and an inner cavity insulating layer of a catheter pump, the curing time at normal temperature is long, and micro cracks exist after curing, and in the use process of the catheter pump, the inner cavity insulating layer is easily corroded to generate gaps and the like under the soaking of fluid for a long time, so that the fluid migrates to coil windings, the coil windings are short-circuited or corroded, and the service life of the motor is shortened. In addition, the catheter pump can be used only after a specific high-temperature sterilization process before being inserted into a human body, so that the epoxy resin material is required to have certain high-temperature resistance, and the situations of deformation of the motor shell due to heating and the like in the high-temperature sterilization process are prevented. Meanwhile, the motor generates certain heat when working, and if the heat is not dissipated in time, the service life of the motor is also influenced, and thrombus can be caused.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a material for manufacturing a catheter pump motor and a preparation method thereof, and the catheter pump motor shell and the inner cavity insulating layer manufactured by using the material have the advantages of short curing time, flat surface of a cured layer body, corrosion resistance, high temperature resistance, good heat dissipation and the like.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a material for manufacturing a catheter pump motor is composed of A, B bi-component, wherein A, B component comprises the following raw materials in parts by weight:
the component A comprises: bisphenol A epoxy resin E5180-100 parts and modified nano SiO21-5 parts of epoxypropane benzyl ether and 2-7 parts of epoxypropane benzyl ether;
and B component: 10-20 parts of polyamide curing agent, 1-4 parts of T31 curing agent, 8-16 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent, 0.5-5 parts of organosilicon coupling agent ND-421-7 parts, silicate filler, 3-9 parts of heat-conducting insulating filler and 9-15 parts of titanium dioxide.
In the invention, modified nano SiO is adopted2Modified nano SiO as the filling material of bisphenol A type epoxy resin2The particles can effectively fill free volume, cracks and the like existing after the material is solidified to improve the barrier property of the inner insulating layer, further prevent the corrosion of fluids such as normal saline or glucose solution and the like to the coil winding through the inner insulating layer, and simultaneously modify the nano SiO2The composite material can be used as a bridge to connect more molecules, so that the cured inner insulating layer is more uniform. However, modified nano SiO2The usage amount of the particles has larger influence on the expected performance after curing if the nano SiO is modified2If the content is too small, the expected effect cannot be achieved, if the nano SiO is modified2The content is too large, and the nano SiO is caused by the agglomeration effect2The tiny cracks cannot be filled due to the increasing size, so that the modified nano SiO is strictly limited in the invention2The amount of (2) used.
In the prior art, only polyamide curing agent is used as the curing agent of epoxy resin in the materials for manufacturing the motor shell and the inner cavity insulating layer of the catheter pump, so that the curing time is long and the performance is single. According to the invention, the polyamide curing agent, the T31 curing agent and the cashew nut shell oil modified phenolic aldehyde amine curing agent are used as the composite curing agent according to a specific proportion, so that a curing system can be rapidly cured at low temperature or normal temperature, the curing time is shortened, the corrosion resistance of the cured material can be enhanced, and fluid immersion is avoided. Wherein, benzene ring structure and bisphenol A type epoxy resin in the cashew nut shell oil modified phenol aldehyde amine curing agent have better compatibility, principal ingredients in the cashew nut shell oil, all have the long side chain of unsaturated C15 in the meta position of phenolic hydroxyl, the hydrophobicity can be improved to the C15 long chain, also make the fixed line system have better pliability, phenolic hydroxyl acidity is stronger, polarization epoxy group that can be easier, catalytic effect to epoxy group and amino reaction is better in the curing process, make the curing system also can fast cure under low temperature or normal atmospheric temperature.
The organic silicon coupling agent ND-42 is used as a curing accelerator, silicate is used as a high-temperature resistant filler, an ideal cross-linking state is formed between the filler and bisphenol A epoxy resin in the presence of a silane coupling agent, the mechanical property is better after curing, SiO formed along with the decomposition of the resin can further react with the filler to form a new structure in the high-temperature sterilization process, and the high-temperature resistance is greatly improved.
Silicon nitride, alumina and silicon carbide are used as mixed fillers, a heat conduction path or a heat conduction network chain can be formed in the curing process, the heat dissipation performance of the material is improved, the heat generated inside the motor is timely dissipated, and the phenomenon that the heat inside the motor is too high to cause failure and further the working stop of the catheter pump seriously affects the service life of a patient is avoided.
Preferably, the A, B component of the material comprises the following raw materials in parts by weight:
the component A comprises: bisphenol A epoxy resin E5186-94 parts and modified nano SiO22-4 parts of epoxypropane benzyl ether and 4-6 parts of epoxypropane benzyl ether;
and B component: 13-16 parts of polyamide curing agent, 2-3 parts of T31 curing agent, 11-14 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent, 6-6 parts of organosilicon coupling agent ND-423, 2-4 parts of silicate filler, 5-8 parts of heat-conducting insulating filler and 11-13 parts of titanium dioxide.
Further, the heat-conducting insulating filler is prepared from silicon nitride, aluminum oxide and silicon carbide according to the mass ratio of (2-7): (4-10) and (1-3) are evenly mixed to obtain the product.
Preferably, the A, B component of the material comprises the following raw materials in parts by weight:
the component A comprises: bisphenol A epoxy resin E5190 parts and modified nano SiO 23 parts of propylene oxide benzyl ether and 5 parts of propylene oxide benzyl ether;
and B component: 15 parts of polyamide curing agent, 3 parts of T31 curing agent, 12 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent, ND-425 parts of organic silicon coupling agent, 3 parts of silicate filler, 12 parts of titanium dioxide and 6 parts of heat-conducting insulating filler, wherein the heat-conducting insulating filler is prepared from silicon nitride, aluminum oxide and silicon carbide according to the mass ratio of 5: 5:2, and mixing uniformly.
Wherein, the modified nano SiO2The preparation method comprises the following steps: mixing nano SiO2Drying the particles in a 120-140 ℃ vacuum drying box for 4-6h, transferring the particles into a three-neck flask, adding hexamethyldisilazane, reacting for 17-19h at 55-65 ℃, transferring the particles into a beaker, placing the beaker into a fume hood, transferring the beaker into a vacuum drying box after air drying, drying for 40-48h at 85-95 ℃, removing unreacted hexamethyldisilazane to obtain modified nano SiO2。
Preferably, nano SiO2And the mass ratio of hexamethyldisilazane is 1: 1.2-1.8.
Preferably, modified nano SiO2The preparation method comprises the following steps: mixing nano SiO2Drying the granules in a vacuum drying oven at 130 ℃ for 6h, transferring the dried granules into a three-neck flask, and adding nano SiO2Hexamethyldisilazane with the mass 1.5 times of that of the precursor reacts for 18h at the temperature of 60 ℃, then the hexamethyldisilazane is transferred to a beaker and placed in a fume hood, the hexamethyldisilazane is transferred to a vacuum drying oven after air drying, dried for 46h at the temperature of 90 ℃, and unreacted hexamethyldisilazane is removed, so that modified nano SiO is obtained2。
The preparation method of the material for manufacturing the catheter pump motor comprises the following steps:
1) bisphenol A type epoxy resin E51 and modified nano SiO2Mixing the epoxypropane benzyl ether according to a certain proportion, and putting the mixture into an ultrasonic cell crusher for ultrasonic treatment for 3-4min to obtain a component A;
2) mixing a polyamide curing agent, a T31 curing agent and a cashew nut shell oil modified phenolic aldehyde amine curing agent in proportion, dispersing at a high speed for 5-10min, adding an organic silicon coupling agent and titanium dioxide, dispersing at a high speed for 3-8min, sequentially adding a silicate filler and a heat-conducting insulating filler, and stirring for 20-30min to obtain a component B;
3) the component A and the component B are independently packaged, and are uniformly mixed according to the mass ratio of 1.5:1 when in use.
(III) advantageous effects
The invention provides a material for manufacturing a catheter pump motor and a preparation method thereof, wherein bisphenol A type epoxy resin E51 and modified nano SiO are used2The epoxy propane benzyl ether, the polyamide curing agent, the T31 curing agent, the cashew nut shell oil modified phenolic aldehyde amine curing agent, the organosilicon coupling agent ND-42, the silicate filler, the heat-conducting insulating filler and the titanium dioxide raw material are compounded and used according to a certain proportion, so that the curing time is effectively shortened, the cured surface is smooth, the generation of internal micro cracks after curing is reduced to the maximum extent, the manufacturing efficiency of the motor is improved, meanwhile, a motor shell and an inner cavity insulating layer formed after the materials are cured have excellent anti-corrosion performance and good high-temperature resistance, heat dissipation and electric insulation performance, the service life of the motor and even a catheter pump is greatly prolonged, and a longer life cycle is obtained for a patientProviding the possibility.
Drawings
In order to more clearly illustrate the technical solutions of the prior art of the present invention, the drawings used in the description of the prior art will be briefly described below.
FIG. 1 is a schematic view of a prior art catheter pump.
Fig. 2 is a schematic diagram of a motor in the prior art.
In the figure: 1-catheter, 2-motor, 3-blood outlet, 4-cannula, 5-blood inlet, 6-pigtail, 2.1-motor shell and inner cavity insulating layer, 2.2-coil, 2.3-stator, 2.4-rotor, 2.5-rotating shaft, 2.6-bearing, 7-axial flow impeller and 8-fluid.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the sources of the raw materials used are shown in Table 1.
Table 1:
raw materials | Source |
Bisphenol A type epoxy resin E51 | Wuxi Xin Yehao chemical Co Ltd |
Nano SiO22(average particle diameter 20nm) | Hangzhou Wanjing new material |
Hexamethyldisilazane | Hangzhou silicon chemical industry Co Ltd |
Cashew nut shell oil modified phenolic aldehyde amine curing agent | Feicheng Delaware chemical Co., Ltd |
T31 curing agent | Feicheng Delaware chemical Co., Ltd |
Polyamide curing agent | Feicheng Delaware chemical Co., Ltd |
Propylene oxide benzyl ether | GUANGZHOU HUIPU NEW MATERIAL Co.,Ltd. |
Organosilicon coupling agent ND-42 | Kazakh Silicone science and technology Co Ltd |
Silicate filler | Shandong Yutai chemical Co Ltd |
Titanium dioxide | Hangzhou silicon treasure chemical Co., Ltd |
Silicon nitride | Hangzhou silicon chemical industry Co Ltd |
Alumina oxide | Hangzhou silicon treasure chemical Co., Ltd |
Silicon carbide | Hangzhou silicon chemical industry Co Ltd |
Examples 1 to 5:
the materials and the preparation methods related to the embodiments 1 to 5 of the invention have the formula shown in the table 2, wherein the modified nano SiO2The preparation method comprises the following steps: mixing nano SiO2Drying the granules in a vacuum drying oven at 130 ℃ for 6h, transferring the dried granules into a three-neck flask, and adding nano SiO2Hexamethyldisilazane with the mass 1.5 times of that of the precursor reacts for 18h at the temperature of 60 ℃, then the hexamethyldisilazane is transferred to a beaker and placed in a fume hood, the hexamethyldisilazane is transferred to a vacuum drying oven after air drying, dried for 46h at the temperature of 90 ℃, and unreacted hexamethyldisilazane is removed, so that modified nano SiO is obtained2。
The preparation method of the material for manufacturing the catheter pump motor comprises the following steps of:
1) bisphenol A type epoxy resin E51 and modified nano SiO2Mixing the epoxypropane benzyl ether in proportion, and putting the mixture into an ultrasonic cell crusher for ultrasonic treatment for 4min to obtain a component A;
2) mixing a polyamide curing agent, a T31 curing agent and a cashew nut shell oil modified phenolic aldehyde amine curing agent in proportion, dispersing at a high speed for 8min, adding an organic silicon coupling agent and titanium dioxide, dispersing at a high speed for 5min, sequentially adding a silicate filler and a heat-conducting insulating filler, and stirring for 25min to obtain a component B;
3) the component A and the component B are independently packaged, and are uniformly mixed according to the mass ratio of 1.5:1 when in use.
Comparative examples 1 to 5:
comparative examples 1 to 5 relate to the material formulations shown in table 2, wherein the sources and preparation methods of the respective raw materials are the same as those of the examples.
Table 2: weight ratio (g) of each component in examples 1 to 5 and comparative examples 1 to 5
And (3) performance testing:
the materials prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to the following performance tests, and the results thereof are shown in Table 3.
Table 3:
in summary, the embodiment of the invention has the following beneficial effects: the materials prepared in the embodiments 1 to 5 of the invention have the advantages of short curing time, corrosion resistance, high temperature resistance, good heat dissipation, good insulation property and the like. As can be seen from Table 3, the materials prepared in comparative examples 1-5 are slightly different in properties from the materials prepared in examples 1-5, further illustrating the modified nano SiO in the composition2T31 curing agent, cashew nut shell oil modified phenolic aldehyde amine curing agent, organosilicon coupling agent ND-42, silicate filler, silicon nitride, alumina, silicon carbide and the like.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A material for manufacturing a catheter pump motor is composed of A, B bi-components, and is characterized in that the A, B component comprises the following raw materials in parts by weight:
the component A comprises: bisphenol A epoxy resin E5180-100 parts of modified nano SiO21-5 parts of epoxypropane benzyl ether and 2-7 parts of epoxypropane benzyl ether;
and B component: 10-20 parts of polyamide curing agent, 1-4 parts of T31 curing agent, 8-16 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent, 0.5-5 parts of organosilicon coupling agent ND-421-7 parts, silicate filler, 3-9 parts of heat-conducting insulating filler and 9-15 parts of titanium dioxide;
the heat-conducting insulating filler is prepared from silicon nitride, aluminum oxide and silicon carbide according to the mass ratio (2-7): (4-10) mixing (1-3) uniformly;
the modified nano SiO2The preparation method comprises the following steps: mixing nano SiO2Drying the particles in a 120-140 ℃ vacuum drying oven for 4-6h, transferring the particles into a three-neck flask, adding hexamethyldisilazane, reacting at 55-65 ℃ for 17-19h, transferring the particles into a beaker, placing the beaker in a fume hood, transferring the beaker into a vacuum drying oven after air drying, drying the beaker at 85-95 ℃ for 40-48h, and removing unreacted hexamethyldisilazane to obtain the modified nano SiO2。
2. A material for manufacturing a catheter pump motor according to claim 1, wherein the A, B component comprises the following raw materials in parts by weight:
the component A comprises: bisphenol A epoxy resin E5186-94 parts and modified nano SiO22-4 parts of epoxypropane benzyl ether and 4-6 parts of epoxypropane benzyl ether;
and B component: 13-16 parts of polyamide curing agent, 2-3 parts of T31 curing agent, 11-14 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent, 6-6 parts of organosilicon coupling agent ND-423, 2-4 parts of silicate filler, 5-8 parts of heat-conducting insulating filler and 11-13 parts of titanium dioxide.
3. A material for manufacturing a catheter pump motor according to claim 1, wherein the A, B component comprises the following raw materials in parts by weight:
the component A comprises: bisphenol A epoxy resin E5190 parts and modified nano SiO23 parts of propylene oxide benzyl ether and 5 parts of propylene oxide benzyl ether;
and B component: 15 parts of polyamide curing agent, 3 parts of T31 curing agent, 12 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent, ND-425 parts of organic silicon coupling agent, 3 parts of silicate filler, 12 parts of titanium dioxide and 6 parts of heat-conducting insulating filler, wherein the heat-conducting insulating filler is prepared from silicon nitride, aluminum oxide and silicon carbide according to the mass ratio of 5: 5:2, and mixing uniformly.
4. The material for manufacturing a catheter pump motor according to claim 1, wherein the nano SiO is2And the mass ratio of hexamethyldisilazane is 1: 1.2-1.8.
5. The material for manufacturing a catheter pump motor according to claim 1, wherein the modified nano SiO is2The preparation method comprises the following steps: mixing nano SiO2Drying the granules in a vacuum drying oven at 130 ℃ for 6h, transferring the dried granules into a three-neck flask, and adding nano SiO2Hexamethyldisilazane with the mass 1.5 times of that of the precursor reacts for 18h at the temperature of 60 ℃, then the hexamethyldisilazane is transferred to a beaker and placed in a fume hood, the hexamethyldisilazane is transferred to a vacuum drying oven after air drying, dried for 46h at the temperature of 90 ℃, and unreacted hexamethyldisilazane is removed, so that modified nano SiO is obtained2。
6. A material for manufacturing a catheter pump motor according to any one of claims 1 to 5, characterized in that the material is prepared by a method comprising the steps of:
1) bisphenol A type epoxy resin E51 and modified nano SiO2Mixing the epoxypropane benzyl ether according to a certain proportion, and putting the mixture into an ultrasonic cell crusher for ultrasonic treatment for 3-4min to obtain a component A;
2) mixing a polyamide curing agent, a T31 curing agent and a cashew nut shell oil modified phenolic aldehyde amine curing agent in proportion, dispersing at a high speed for 5-10min, adding an organic silicon coupling agent and titanium dioxide, dispersing at a high speed for 3-8min, sequentially adding a silicate filler and a heat-conducting insulating filler, and stirring for 20-30min to obtain a component B;
3) the component A and the component B are independently packaged, and are uniformly mixed according to the mass ratio of 1.5:1 when in use.
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