技术领域Technical field
本发明涉及医疗器械领域，具体涉及一种球囊导管。The invention relates to the field of medical devices, and in particular to a balloon catheter.
背景技术Background technique
治疗脑血管疾病的神经介入技术已经在临床中进行了广泛的应用。近年来，随着影像学设备的进步、治疗理念的创新性发展，各类新型介入器械为神经介入医生提供了更多可选的治疗手段，使医生可以处理越来越多的复杂的病变。Neurointerventional technology for the treatment of cerebrovascular diseases has been widely used in clinical practice. In recent years, with the advancement of imaging equipment and innovative development of treatment concepts, various new interventional devices have provided neurointerventional doctors with more optional treatment methods, allowing doctors to treat more and more complex lesions.
近年来，机械取栓成为治疗缺血性脑卒中的重要手段，其原理是通过抽吸导管或取栓支架等治疗性器械完成对血栓的抽吸或抓取，从而完成对血管中的堵塞血栓的清除，达到血管再通的治疗目的。球囊导引导管作为一种新型的通路器械，可以辅助取栓器械更好地完成血栓的清除，降低血栓被血液冲至血管更远端的风险。球囊导引导管经由血管鞘入路，辅助取栓器械到达病变血管近端后，通过在导管近端球囊腔道内注入液体，将导管远端的球囊膨开，使其紧贴血管壁，形成对该处血管的短暂封堵，防止血液对血栓形成冲击，降低血栓向更远处逃逸的风险。相比用于扩张狭窄的球囊扩张导管所用的非顺应性球囊，球囊导引导管所用的球囊为顺应性球囊或半顺应球囊。In recent years, mechanical thrombectomy has become an important method for the treatment of ischemic stroke. Its principle is to complete the suction or capture of thrombus through therapeutic devices such as suction catheters or thrombectomy stents, thereby completing the removal of clogged thrombi in blood vessels. removal to achieve the therapeutic purpose of vascular recanalization. As a new type of access device, the balloon guiding catheter can assist the thrombectomy device to better remove thrombus and reduce the risk of thrombus being flushed by blood to the more distal part of the blood vessel. The balloon guiding catheter is passed through the vascular sheath. After the auxiliary thrombectomy instrument reaches the proximal end of the diseased blood vessel, liquid is injected into the balloon lumen at the proximal end of the catheter to expand the balloon at the distal end of the catheter to make it close to the blood vessel wall. , forming a temporary blockage of the blood vessel, preventing the blood from impacting the thrombus, and reducing the risk of the thrombus escaping farther away. Compared to the non-compliant balloons used in balloon dilatation catheters used to dilate stenoses, the balloons used in balloon guide catheters are compliant or semi-compliant balloons.
相比扩张狭窄的球囊扩张导管不需要内通器械，球囊导引导管同时有到位和通过器械的需求，因此需要较小的外径和较大的内径，然而在现有技术中，顺应性或半顺应性球囊常用材质为硅胶、乳胶等，上述材质与常用的医用材料相容性差，球囊只能采用胶水粘接的方式与内管和外管固定，胶水的使用造成球囊处的外径偏大，外径偏大会造成球囊导管到位能力差。此外，导管粘接处的软硬过渡不顺滑，也会影响球囊导引导管的到位性，较差的软硬过渡使得球囊导引导管在通过迂曲的血管时，存在更大的损伤血管内壁的风险，造成患者的不适感。Compared with the balloon dilation catheter that dilates stenosis, it does not require internal communication instruments. The balloon guidance catheter has the need to be in place and pass the instrument at the same time, so it requires a smaller outer diameter and a larger inner diameter. However, in the existing technology, compliance Commonly used materials for flexible or semi-compliant balloons are silicone, latex, etc. The above materials have poor compatibility with commonly used medical materials. The balloon can only be fixed to the inner and outer tubes by glue bonding. The use of glue causes the balloon to If the outer diameter is too large, the outer diameter will cause poor ability of the balloon catheter to be in place. In addition, the soft-hard transition at the catheter bonding point is not smooth, which will also affect the positioning of the balloon guiding catheter. Poor soft-hard transition will cause greater damage to the balloon guiding catheter when passing through tortuous blood vessels. Risk to the inner wall of blood vessels, causing discomfort to the patient.
聚氨酯是一种具有优异的高弹性及弹性变形率的一类材料，其广泛应用于生物医用领域，具有良好的生物相容性的优势。聚氨酯相比于硅胶材料具有良好的材料相容性，其可通过热熔与常用医用材料如PE、Pebax、Nylon等进行粘接。此外，聚氨酯还是亲水涂层的良好基底，可对导管及球囊处进行涂层。但是，在具有相同耐压强度及弹性变形能力的情况下，聚氨酯材料相比于硅胶材料硬度更高。因此，聚氨酯没有广泛作为球囊材料进行使用。Polyurethane is a type of material with excellent high elasticity and elastic deformation rate. It is widely used in the biomedical field and has the advantage of good biocompatibility. Compared with silicone materials, polyurethane has good material compatibility, and it can be bonded to common medical materials such as PE, Pebax, Nylon, etc. through hot melt. In addition, polyurethane is a good base for hydrophilic coatings on catheters and balloons. However, with the same compressive strength and elastic deformation ability, polyurethane materials are harder than silicone materials. Therefore, polyurethane is not widely used as a balloon material.
需要说明的是，公开于该发明背景技术部分的信息仅仅旨在加深对本发明一般背景技术的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。It should be noted that the information disclosed in the background technology section of this invention is only intended to deepen the understanding of the general background technology of the invention, and should not be regarded as an admission or any form of implication that the information constitutes what is already known to those skilled in the art. current technology.
发明内容Contents of the invention
针对上述技术问题，本发明的目的在于提供一种球囊导管，可以解决现有技术中球囊导管的球囊材料不能同时满足力学强度、顺应性和粘接性的要求，使球囊在使用中可以满足临床需求；同时，进一步解决导管主体和球囊连接处外径偏大的问题，使连接处软硬过渡顺滑，提高球囊导管的到位能力。In view of the above technical problems, the purpose of the present invention is to provide a balloon catheter that can solve the problem that the balloon material of the balloon catheter in the prior art cannot meet the requirements of mechanical strength, compliance and adhesiveness at the same time, so that the balloon can be used It can meet clinical needs; at the same time, it further solves the problem of the large outer diameter of the connection between the catheter body and the balloon, making the connection smooth between soft and hard, and improving the ability of the balloon catheter to be put in place.
为了实现上述目的，本发明提供一种球囊导管，包括：导管主体、球囊，所述球囊套设并连接于导管主体，所述球囊的材料包括通式a所表示的高分子：In order to achieve the above object, the present invention provides a balloon catheter, which includes: a catheter body and a balloon; the balloon is sleeved and connected to the catheter body; the material of the balloon includes a polymer represented by the general formula a:
其中，R1和R2相互独立选自芳基或带芳基的链段，R3为碳原子数大于等于4的烷基。Among them, R1 and R2 are independently selected from an aryl group or a chain segment with an aryl group, and R3 is an alkyl group with 4 or more carbon atoms.
可选地，所述m的范围为4-28。Optionally, the range of m is 4-28.
可选地，所述n的范围为2-6。Optionally, the range of n is 2-6.
可选地，所述x的范围为100-190。Optionally, the range of x is 100-190.
可选地，所述y的范围为150-285。Optionally, the range of y is 150-285.
可选地，x：y的范围为1:3～2:1。Optionally, the range of x:y is 1:3~2:1.
可选地，所述R1与R2的结构相同。Optionally, the structures of R1 and R2 are the same.
可选地，所述R1与R2相互独立选自单苯芳环、邻苯芳环、萘、芴。Alternatively, R1 and R2 are independently selected from the group consisting of monobenzene aromatic ring, o-phenyl aromatic ring, naphthalene, and fluorene.
可选地，所述R1和/或R2的结构式为：Optionally, the structural formula of R1 and/or R2 is:
可选地，所述R1和/或R2的结构式为：Optionally, the structural formula of R1 and/or R2 is:
可选地，所述球囊的材料的断裂延伸率大于800％。Optionally, the material of the balloon has an elongation at break greater than 800%.
可选地，所述球囊的材料的硬度为40A～60A。Optionally, the hardness of the balloon material is 40A to 60A.
可选地，所述球囊的厚度为0.002inch～0.004inch。Optionally, the thickness of the balloon is 0.002 inch to 0.004 inch.
可选地，所述球囊的材料的重均分子量为150000～200000DA。Optionally, the weight average molecular weight of the balloon material is 150,000 to 200,000 DA.
可选地，所述导管主体包括从内到外依次套设的内管和外管，所述内管的远端从所述外管的远端开口穿出，所述球囊的近端与所述外管的外表面连接，所述球囊的远端与所述内管的外表面连接。Optionally, the catheter body includes an inner tube and an outer tube that are sleeved in sequence from the inside to the outside. The distal end of the inner tube passes through the distal opening of the outer tube, and the proximal end of the balloon is connected to the distal opening of the outer tube. The outer surface of the outer tube is connected, and the distal end of the balloon is connected with the outer surface of the inner tube.
可选地，所述内管和/或所述外管在与所述球囊连接的位置对应的材料为线性低密度聚乙烯。Optionally, the material of the inner tube and/or the outer tube corresponding to the position connected to the balloon is linear low density polyethylene.
可选地，所述线性低密度聚乙烯经马来酸酐接枝。Optionally, the linear low density polyethylene is grafted with maleic anhydride.
本发明还提供一种制备球囊导管的方法，包括，所述球囊与所述导管主体之间通过热熔焊接工艺进行连接。The present invention also provides a method for preparing a balloon catheter, which includes connecting the balloon and the catheter body through a hot melt welding process.
可选地，所述球囊与所述导管主体之间通过热熔焊接工艺进行连接。Optionally, the balloon and the catheter body are connected through a hot melt welding process.
可选地，所述热熔焊接工艺为激光焊接。Optionally, the hot melt welding process is laser welding.
在本发明提供的球囊导管包括：导管主体、球囊，所述球囊套设并连接于导管主体，所述球囊的材料包括通式a所表示的高分子：The balloon catheter provided by the present invention includes: a catheter body and a balloon; the balloon is sleeved and connected to the catheter body; the material of the balloon includes a polymer represented by the general formula a:
其中，R1和R2相互独立选自芳基或带芳基的链段，R3为碳原子数大于等于4的烷基。该球囊导管至少具有以下优势：Among them, R1 and R2 are independently selected from an aryl group or a chain segment with an aryl group, and R3 is an alkyl group with 4 or more carbon atoms. This balloon catheter has at least the following advantages:
1.球囊具有良好的弹性变形率及弹性回复性能。1. The balloon has good elastic deformation rate and elastic recovery performance.
2.相比常见的球囊材料，如硅胶，所选材料是亲水涂层的优良基底，亲水涂层牢固度高，不易脱落。2. Compared with common balloon materials, such as silica gel, the selected material is an excellent base for hydrophilic coating. The hydrophilic coating has high firmness and is not easy to fall off.
3.所选材料与其他常用的医用高分子材料的相容性好，球囊与导管主体的连接处不需要使用胶水，使连接处的外径较小，可以到达更细的血管的位置。3. The selected material has good compatibility with other commonly used medical polymer materials. No glue is needed at the connection between the balloon and the catheter body, which makes the outer diameter of the connection smaller and can reach the location of thinner blood vessels.
4.通过热熔焊接的球囊与导管主体之间的连接强度高，在充盈过程或者输送过程中不容易脱落。4. The connection between the hot-melt welded balloon and the main body of the catheter is high and will not easily fall off during the filling or transportation process.
5.球囊与导管主体的连接处软硬过渡顺滑，提高导管的到位能力，同时在通过迂曲血管时，不容易损伤血管。5. The connection between the balloon and the main body of the catheter has a smooth transition from soft to hard, which improves the catheter's ability to be placed in place. At the same time, it is not easy to damage blood vessels when passing through tortuous blood vessels.
6.球囊的断裂延伸率高，顺应好，膨胀后更容易贴合血管，封堵效果好。6. The balloon has a high elongation at break and good compliance. After expansion, it is easier to fit the blood vessel and has a good blocking effect.
附图说明Description of drawings
本发明提供的附图并不需要按比例画图，且一些部件和结构为了清楚而扩大。可以考虑图示实施例的变化形式。因此，在附图中的实施例的多个方面和元件的介绍并不用于限制本发明的范围。在附图中：The drawings provided herein are not necessarily drawn to scale, and some components and structures are exaggerated for clarity. Variations of the illustrated embodiments are contemplated. Therefore, the presentation of aspects and elements of the embodiments in the drawings is not intended to limit the scope of the invention. In the attached picture:
图1为本发明根据实施例提供的球囊导管的轴向截面图；Figure 1 is an axial cross-sectional view of a balloon catheter provided according to an embodiment of the present invention;
图2为本发明根据实施例提供的球囊导管的球囊材料的一示例性分子结构式；Figure 2 is an exemplary molecular structural formula of the balloon material of the balloon catheter provided according to an embodiment of the present invention;
图3为本发明根据实施例提供的球囊导管的球囊材料的一示例性分子结构式；Figure 3 is an exemplary molecular structural formula of the balloon material of the balloon catheter provided according to an embodiment of the present invention;
图4为本发明根据实施例提供的不同球囊材料的拉伸回弹测试的测试结果。Figure 4 is the test results of the tensile rebound test of different balloon materials provided according to the embodiment of the present invention.
图5为本发明根据实施例提供的不同球囊材料的断裂延伸率和200％拉伸变形率下压力值的测试结果。Figure 5 is a test result of the elongation at break and the pressure value at 200% tensile deformation rate of different balloon materials according to embodiments of the present invention.
图6为本发明根据实施例提供的球囊导管的球囊材料硬度对充盈和回抽过程的影响；Figure 6 shows the effect of the hardness of the balloon material of the balloon catheter provided according to the embodiment of the present invention on the filling and withdrawal processes;
附图中：In the attached picture:
1-导管主体；2-球囊；11-外管；12-内管；1-catheter body; 2-balloon; 11-outer tube; 12-inner tube;
具体实施方式Detailed ways
下面将介绍各种示例实施例。这些实例为非限定的，应当知道，它们用于示例说明装置、系统和方法的更广义应用方面。在不脱离本发明的真正精神和范围的情况下，这些实施例可以进行多种变化，且可以由等效物代替。此外，可以进行多种变化，以便适应特殊的情况、材料、物质组分、处理、处理动作或步骤来适应本发明的目的、精神或范围。所有这些变化都将在本发明的保护范围内。Various example embodiments are described below. These examples are non-limiting and it is understood that they are intended to illustrate the broader applications of the devices, systems and methods. Various changes may be made to these embodiments and equivalents may be substituted without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, process, process act or step to the purpose, spirit or scope of the invention. All such variations are intended to be within the scope of the present invention.
对于在概述或详细说明中介绍的任何尺寸，它们将只是实例，并不是限制本发明主题，除非在各种示例实施例中提出。而且，本文中所述的实施例的多种结构将彼此补充，而不是纯粹交替，除非这样说明。换句话说，来自一个实施例的结构可以与其它实施例的结构自由地组合，如本领域普通技术人员很容易知道，除非说明这些结构只用于替换。To the extent that any dimensions are introduced in the summary or detailed description, they are intended to be examples only and not limiting of the subject matter except as set forth in the various exemplary embodiments. Furthermore, the various structures of the embodiments described herein are intended to complement each other and not purely alternate unless otherwise indicated. In other words, structures from one embodiment may be freely combined with structures from other embodiments, as would be readily apparent to one of ordinary skill in the art, unless stated that these structures are only for substitution.
在本申请文件中，“轴向”通常指平行于球囊导管的中心轴线的方向；“径向”通常指球囊导管的直径方向，也即与中心轴线垂直的方向；“周向”通常指围绕球囊导管的中心轴线的方向。在本申请文件中，“内”是指靠近球囊导管的内表面的一侧；“外”是指靠近球囊导管的外表面的一侧；沿球囊导管的内表面到外表面方向的尺寸定义为厚度。“近端”通常是指靠近介入系统操作者的一端，“远端”与“近端”相对，是指远离介入系统操作者的一端。In this application document, "axial" usually refers to the direction parallel to the central axis of the balloon catheter; "radial" usually refers to the diameter direction of the balloon catheter, that is, the direction perpendicular to the central axis; "circumferential" usually refers to the direction perpendicular to the central axis of the balloon catheter. Refers to the direction around the central axis of the balloon catheter. In this application document, "inner" refers to the side close to the inner surface of the balloon catheter; "outer" refers to the side close to the outer surface of the balloon catheter; along the direction from the inner surface to the outer surface of the balloon catheter Dimension is defined as thickness. The "proximal end" usually refers to the end close to the operator of the interventional system, and the "distal end" is opposite to the "proximal end" and refers to the end far away from the operator of the interventional system.
以下参考附图和优选实施例对本发明作进一步的说明，且在不冲突的情况下，下述的实施方式及实施方式中的特征可以相互补充或相互组合。The present invention will be further described below with reference to the accompanying drawings and preferred embodiments, and the following embodiments and features in the embodiments may complement or be combined with each other unless they conflict.
【实施例一】[Example 1]
请参考图1，本申请实施例一提供一种球囊导管，其包括：导管主体1、球囊2，球囊2套设并连接于导管主体1，球囊2的材料包括通式a所表示的高分子：Please refer to Figure 1. Embodiment 1 of the present application provides a balloon catheter, which includes: a catheter body 1 and a balloon 2. The balloon 2 is sleeved and connected to the catheter body 1. The material of the balloon 2 includes the general formula a Represented polymer:
其中，R1和R2相互独立选自芳基或带芳基的链段，R3为碳原子数大于等于4的烷基。Among them, R1 and R2 are independently selected from an aryl group or a chain segment with an aryl group, and R3 is an alkyl group with 4 or more carbon atoms.
通式a所表示的高分子具有高弹性、高强度、高韧性，并能与常用的医用高分子材料通过热熔焊接工艺粘接，热熔焊接工艺包括热缩工艺、激光焊接工艺、热焊接工艺等。采用通式a所表示的高分子制备的球囊2具有较好的顺应性、较高的断裂延伸率、良好的弹性变形率及弹性回复性能且弹性好、爆破压高，能满足球囊导管封堵血管、输送到位的需求，膨胀后更容易贴合血管，封堵效果好。此外，由于通式a所表示的高分子能与常用的医用高分子通过热熔工艺焊接，避免了在球囊2与导管主体1的连接处使用胶水，使球囊导管在球囊2与导管主体1的连接处的整体外径较小，在保证球囊导管的内径足够大的同时，实现较小的外径，同时满足了球囊导管的到位需求和内通器械的需求，且通过热熔粘接的球囊2与导管主体1之间的连接强度高，在充盈过程或者输送过程中不容易脱落，热熔焊接工艺还使得球囊2与导管主体1的连接处软硬过渡顺滑，提高导管的到位能力，在通过迂曲血管时，不容易损伤血管。同时，由于通式a所表示的高分子是亲水涂层的优良基底，容易对其表面进行涂层，且涂覆的亲水涂层牢固度高，不易脱落，在球囊2表面进行亲水涂层可以进一步提高球囊导引导管的到位性能、减小在封堵血管时对血管的损伤。The polymer represented by general formula a has high elasticity, high strength, and high toughness, and can be bonded to commonly used medical polymer materials through hot melt welding processes. Hot melt welding processes include heat shrinkage, laser welding, and thermal welding. Craftsmanship etc. The balloon 2 prepared by using the polymer represented by the general formula a has good compliance, high elongation at break, good elastic deformation rate and elastic recovery performance, good elasticity and high burst pressure, and can meet the needs of balloon catheters. For the needs of blocking blood vessels and delivering them in place, it is easier to fit the blood vessels after expansion, and the blocking effect is good. In addition, since the polymer represented by the general formula a can be welded with commonly used medical polymers through a hot melt process, the use of glue at the connection between the balloon 2 and the catheter body 1 is avoided, allowing the balloon catheter to be connected between the balloon 2 and the catheter The overall outer diameter of the connection of the main body 1 is small, which ensures that the inner diameter of the balloon catheter is large enough while achieving a smaller outer diameter, while meeting the needs of the balloon catheter in place and the internal communication device, and through the heat The connection between the melt-bonded balloon 2 and the catheter body 1 has high strength and is not easy to fall off during the filling or transportation process. The hot-melt welding process also makes the soft-hard transition between the balloon 2 and the catheter body 1 smooth. , improve the ability of the catheter to be in place, and will not easily damage the blood vessels when passing through tortuous blood vessels. At the same time, since the polymer represented by the general formula a is an excellent base for the hydrophilic coating, it is easy to coat its surface, and the coated hydrophilic coating has high firmness and is not easy to fall off. The water coating can further improve the placement performance of the balloon guidance catheter and reduce damage to blood vessels when blocking blood vessels.
需要说明的是，“芳基”应被理解为指具有至少一个芳环的基团。例如为苯基、萘基、荧蒽基、芴基、苯并芴基、蒽基、萘满基、茚满基、吡咯基、咪唑基、吡唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基、异吲哚基、吲哚基、吲唑基、嘌呤基等。所述芳环可以为未取代、单取代或多取代。通式a所表示的高分子中的R1和/或R2限定为芳基或带芳基的链段，可以提高球囊材料的粘接性能，且材料不容易老化。因此相比常见的球囊材料所制备的球囊2，如硅胶，球囊2与导管主体1的连接处不需要使用胶水，连接处的外径较小，且球囊2与导管主体1之间的连接强度高，在充盈过程或者输送过程中不容易脱落。优选的，R1与R2相互独立选自单苯芳环、邻苯芳环、萘、芴。优选的，R1与R2的结构相同。当然，在一些实施例中，R1与R2的结构也可以不同。It should be noted that "aryl" should be understood to mean a group having at least one aromatic ring. For example, phenyl, naphthyl, fluoranthyl, fluorenyl, benzofluorenyl, anthracenyl, tetralinyl, indanyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl , pyridazinyl, isoindolyl, indolyl, indazolyl, purinyl, etc. The aromatic ring may be unsubstituted, monosubstituted or polysubstituted. R1 and/or R2 in the polymer represented by the general formula a is limited to an aryl group or a segment with an aryl group, which can improve the bonding performance of the balloon material and make the material less likely to age. Therefore, compared with the balloon 2 made of common balloon materials, such as silicone, the connection between the balloon 2 and the catheter body 1 does not require the use of glue, the outer diameter of the connection is smaller, and the connection between the balloon 2 and the catheter body 1 The connection strength between them is high and it is not easy to fall off during the filling process or transportation process. Preferably, R1 and R2 are independently selected from monobenzene aromatic ring, o-phenyl aromatic ring, naphthalene, and fluorene. Preferably, R1 and R2 have the same structure. Of course, in some embodiments, the structures of R1 and R2 may also be different.
需要进一步说明的是，虽然通式a表示为二嵌段共聚物的形式，但是如此表示仅仅是为了描述方便，通式a所表示的高分子可以是两段式的二嵌段共聚物，即一种单体形成一个长链段连接另一种单体形成的另一个长链段，也可以是不同单体混合排布的形式的共聚物，例如通式a中左边的链段称为硬段，通式a中右边的链段称为软段，硬段和软段依次混合交替排布，每个硬段和/或每个软段的聚合度不限。It should be further explained that although the general formula a is expressed in the form of a diblock copolymer, this expression is only for the convenience of description. The polymer represented by the general formula a can be a two-stage diblock copolymer, that is One monomer forms a long chain segment connected to another long chain segment formed by another monomer. It can also be a copolymer in the form of a mixed arrangement of different monomers. For example, the chain segment on the left side of the general formula a is called a hard chain segment. Segment, the chain segment on the right side of the general formula a is called a soft segment, and the hard segments and soft segments are mixed and arranged alternately in sequence. The degree of polymerization of each hard segment and/or each soft segment is not limited.
通式a所表示的高分子中的R3限定为碳原子数大于等于4的烷基，可以保证材料具有良好的弹性，且断裂延伸率高，因此采用通式a所表示的高分子制备的球囊2顺应好、具有良好的弹性变形率，膨胀后更容易贴合血管，封堵效果好，且具有良好弹性回复性能，球囊2可以经多次充盈膨胀和回抽收缩，而不影响球囊2的外观和性能。R3 in the polymer represented by the general formula a is limited to an alkyl group with a carbon number of 4 or more, which can ensure that the material has good elasticity and high elongation at break. Therefore, it is prepared by using the polymer represented by the general formula a. The balloon 2 is well compliant and has a good elastic deformation rate. After expansion, it is easier to fit the blood vessel, has a good blocking effect, and has good elastic recovery performance. The balloon 2 can be filled and expanded and withdrawn and contracted for many times without affecting the Balloon 2 appearance and performance.
另外，R1和/或R2限定为芳基或带芳基的链段，以及R3限定为碳原子数大于等于4的烷基，使得所用材料可以通过调控n、m、x、y的数值选择合适的硬度。球囊2的硬度对其性能具有较大的影响，硬度过小，球囊2可能无法较好充盈，充盈过程中会有几率发生偏心现象，若在手术过程中，球囊2发生偏心现象，会造成对血管一侧产生的压力过大，可能会对血管造成损伤，且无法很好地封堵血管；硬度过大，球囊2在充盈过程中也有可能发生偏心或者充盈不充分的现象，且在充盈后回抽过程中可能产生无法复原的情况，即回抽充盈液后，球囊2无法紧贴导管主体1，若在手术过程中，球囊2无法回抽复原，不方便球囊封堵位置的调整，封堵完成后也会影响球囊导管的回撤。因此，通式a所表示的高分子优选硬度为40A～60A。In addition, R1 and/or R2 are limited to an aryl group or a segment with an aryl group, and R3 is limited to an alkyl group with a carbon number of 4 or more, so that the materials used can be adjusted by adjusting n, m, x, y Use the numerical value to select the appropriate hardness. The hardness of the balloon 2 has a great impact on its performance. If the hardness is too small, the balloon 2 may not be properly filled, and there may be a chance of eccentricity during the filling process. If the balloon 2 is eccentric during the operation, It will cause excessive pressure on one side of the blood vessel, which may cause damage to the blood vessel, and the blood vessel cannot be blocked well; if the hardness is too large, the balloon 2 may also be eccentric or insufficiently filled during the filling process. And during the withdrawal process after filling, an irreversible situation may occur, that is, after the filling fluid is withdrawn, the balloon 2 cannot be close to the catheter body 1. If during the operation, the balloon 2 cannot be withdrawn and restored, it will be inconvenient for the balloon. Adjustment of the blocking position will also affect the withdrawal of the balloon catheter after the blocking is completed. Therefore, the polymer represented by the general formula a preferably has a hardness of 40A to 60A.
优选的，通式a所表示的高分子中的m的范围为4-28，例如5、8、10、15、20、25、28。m的值越大，则材料刚度越低，弹性越好，m过大会造成材料过于柔软而使用该材料制备的球囊2在充盈过程中容易偏心，造成球囊2封堵血管时的稳定性差，m过小会造成材料弹性不足，充盈后球囊2的永久变形率较大，影响球囊2的回抽性能，球囊2充盈回抽后无法恢复原始状态，影响球囊2的再次充盈，球囊导管无法反复调整封堵位置。Preferably, the range of m in the polymer represented by general formula a is 4-28, such as 5, 8, 10, 15, 20, 25, 28. The larger the value of m, the lower the material stiffness and the better the elasticity. If m is too large, the material will be too soft and the balloon 2 prepared using this material will be easily eccentric during the filling process, resulting in poor stability of the balloon 2 when blocking blood vessels. , if m is too small, the elasticity of the material will be insufficient, and the permanent deformation rate of the balloon 2 after filling will be large, which will affect the retraction performance of the balloon 2. The balloon 2 will not be able to return to its original state after being filled and retracted, affecting the refilling of the balloon 2. , the balloon catheter cannot repeatedly adjust the blocking position.
优选的，通式a所表示的高分子中的n的范围为2-6，例如2、3、4、5、6。n的值越大，则柔性链段更柔软，其弹性越好，n过大会造成材料的材料过于柔软而造成球囊2偏心且材料抗热老化性能和抗氧老化性能降低，n过小会造成材料硬度变大，充盈后球囊2的永久变形率较大，影响球囊2的回抽性能。Preferably, n in the polymer represented by general formula a ranges from 2 to 6, such as 2, 3, 4, 5, and 6. The larger the value of n, the softer the flexible segment and the better its elasticity. If n is too large, the material will be too soft, causing the balloon 2 to be eccentric and the material's thermal aging resistance and oxidative aging resistance will be reduced. If n is too small, the material will be too soft. As a result, the hardness of the material becomes larger, and the permanent deformation rate of the balloon 2 after inflation is larger, which affects the withdrawal performance of the balloon 2 .
优选的，通式a所表示的高分子中的x的范围为100-190，例如100、120、150、160、180、190。x的值越大，则材料中硬段含量增大，材料的硬度更高，x过大会造成材料弹性形变能力变差，充盈时所需的压力更大，不利于球囊2的弹性形变，过小会造成硬度太低，造成球囊2偏心等问题。Preferably, the range of x in the polymer represented by general formula a is 100-190, such as 100, 120, 150, 160, 180, 190. The larger the value of If it is too small, the hardness will be too low, causing problems such as eccentricity of the balloon 2.
优选的，通式a所表示的高分子中的y的范围为150-285，例如150、160、175、190、200、220、250、270、285。y的值越大，则材料中软段含量增大，材料更柔软，y过大会造成材料过于柔软，y过小会造成硬度过高。Preferably, the range of y in the polymer represented by general formula a is 150-285, such as 150, 160, 175, 190, 200, 220, 250, 270, 285. The larger the value of y, the soft segment content in the material increases and the material becomes softer. If y is too large, the material will be too soft, and if y is too small, the hardness will be too high.
优选的，通式a所表示的高分子中的x：y的范围为1:3～2:1，例,1:3、1：2、1:1、2:1，x：y的值代表着高分子中硬段的数量与软段的数量之比，因此，x：y过大会造成材料过硬，x：y过小会造成材料过软。Preferably, the range of x:y in the polymer represented by the general formula a is 1:3 to 2:1, for example, 1:3, 1:2, 1:1, 2:1, the value of x:y It represents the ratio of the number of hard segments to the number of soft segments in the polymer. Therefore, if x:y is too large, the material will be too hard, and if x:y is too small, the material will be too soft.
此外，作为用于封堵血管的球囊导管，其对材料顺应性的要求较高，顺应性材料在膨胀时能紧贴血管内壁，并可以在膨胀过程中根据血管的形状自动调整球囊2的形状，为了较好地封堵血管，球囊2需要具有较好的延伸率，因此，在本发明中，通式a所表示的高分子优选为具有大于800％的断裂延伸率，即球囊材料具有大于800％的断裂延伸率。若球囊材料的断裂延伸率过小，在球囊2膨胀过程中，有可能发生断裂，从而损伤血管。In addition, as a balloon catheter used to seal blood vessels, it has high requirements for material compliance. The compliant material can adhere closely to the inner wall of the blood vessel during expansion, and can automatically adjust the balloon according to the shape of the blood vessel during the expansion process 2 In order to seal blood vessels better, the balloon 2 needs to have a better elongation. Therefore, in the present invention, the polymer represented by the general formula a preferably has an elongation at break of greater than 800%, that is, the balloon 2 needs to have a better elongation. The bladder material has an elongation at break greater than 800%. If the elongation at break of the balloon material is too small, the balloon 2 may break during the expansion process, thereby damaging the blood vessel.
优选的，球囊2的厚度为0.002inch～0.004inch。球囊2的厚度影响了球囊2的强度和扩张性能，如果球囊2的厚度过大，一方面球囊导管通过迂曲血管的性能差，到位能力差且容易刺激血管，另一方面过厚的球囊2可能导致球囊2的膨胀性能不佳，充盈时膨胀较为困难；如果球囊2的厚度过小，球囊2在充盈时容易发生偏心的现象，且充盈体积较大时容易破裂。Preferably, the thickness of the balloon 2 is 0.002inch to 0.004inch. The thickness of the balloon 2 affects the strength and expansion performance of the balloon 2. If the thickness of the balloon 2 is too large, on the one hand, the performance of the balloon catheter through tortuous blood vessels will be poor, its ability to be in place will be poor, and it is easy to irritate blood vessels. On the other hand, it will be too thick. The balloon 2 may have poor inflation performance, making it difficult to inflate during inflation; if the thickness of the balloon 2 is too small, the balloon 2 may be prone to eccentricity during inflation, and may easily rupture when the inflation volume is large. .
优选的，通式a所表示的高分子的重均分子量为150000～200000DA，例如160000DA、170000DA、180000DA、190000DA，若球囊2所用的高分子分子量过大，高分子的加工性能不佳，加工时流动性差，不容易与其他材料形成共混物，影响球囊2与导管主体1之间的粘接性能；若球囊2所用的高分子分子量过小，其材料的机械性能差，球囊2强度低，球囊2在工艺制备或者使用过程中容易破裂。Preferably, the weight average molecular weight of the polymer represented by the general formula a is 150000 to 200000DA, such as 160000DA, 170000DA, 180000DA, 190000DA. If the molecular weight of the polymer used in the balloon 2 is too large, the processing performance of the polymer will be poor and the processing When the fluidity is poor, it is not easy to form a blend with other materials, which affects the bonding performance between the balloon 2 and the catheter body 1; if the molecular weight of the polymer used in the balloon 2 is too small, the mechanical properties of the material will be poor, and the balloon will 2. The strength is low, and the balloon 2 is easily ruptured during process preparation or use.
如图1所示，导管主体1包括从内到外依次套设的内管12和外管11，内管12的远端从外管11的远端开口穿出，球囊2与导管主体1的连接方式为：球囊2的近端与导管主体1中的外管11的外表面连接，球囊2的远端与导管主体1中的内管12的外表面连接。外管11与内管12之间形成腔道，该腔道用于通过充盈液体使球囊2膨胀。球囊2连接于外管11和内管12之间的方式有效减小了球囊2对导管整体外径的影响，且球囊2与导管主体1之间使用热熔焊接工艺进行连接，球囊2与导管主体1的连接位置避免了胶水的使用，进一步使得球囊2不会对球囊导管整体的外径造成过大的影响，球囊2与导管主体1的连接位置避免了胶水的使用。在该实施方式中，外管11的外径优选≤2.90mm，外管11的内径优选≥2.50mm，内管12的外径优选2.42-2.50mm，内管12的内径优选0.0850-0.0890inch，在该范围内，既能保证导管的外径较小，能通过较为迂曲或者较为细小的血管，又能保证导管的内径够大，可以通过较大的医疗器械，此外，充盈腔的体积也较大，可以保证充盈和回抽球囊2的难度小、速度快。在其他一些实施例中，球囊2的近端和远端都与外管11连接，导管主体1的外管11与内管12在球囊导管的最远端相互连接，外管11和内管12之间形成充液腔提供通过充盈液的通道。As shown in Figure 1, the catheter body 1 includes an inner tube 12 and an outer tube 11 that are sleeved in sequence from the inside to the outside. The distal end of the inner tube 12 passes through the distal opening of the outer tube 11. The balloon 2 is connected to the catheter body 1. The connection method is: the proximal end of the balloon 2 is connected to the outer surface of the outer tube 11 in the catheter body 1, and the distal end of the balloon 2 is connected to the outer surface of the inner tube 12 in the catheter body 1. A lumen is formed between the outer tube 11 and the inner tube 12, and the lumen is used to inflate the balloon 2 by filling it with liquid. The way the balloon 2 is connected between the outer tube 11 and the inner tube 12 effectively reduces the impact of the balloon 2 on the overall outer diameter of the catheter, and the balloon 2 and the catheter body 1 are connected using a hot melt welding process. The connection position between the balloon 2 and the catheter body 1 avoids the use of glue, further preventing the balloon 2 from having an excessive impact on the overall outer diameter of the balloon catheter. The connection position between the balloon 2 and the catheter body 1 avoids the use of glue. use. In this embodiment, the outer diameter of the outer tube 11 is preferably ≤2.90mm, the inner diameter of the outer tube 11 is preferably ≥2.50mm, the outer diameter of the inner tube 12 is preferably 2.42-2.50mm, and the inner diameter of the inner tube 12 is preferably 0.0850-0.0890inch. Within this range, it can ensure that the outer diameter of the catheter is small enough to pass through more tortuous or smaller blood vessels, and the inner diameter of the catheter is large enough to pass through larger medical devices. In addition, the volume of the filling cavity is also relatively small. It is large and can ensure that filling and withdrawing the balloon 2 are less difficult and faster. In some other embodiments, the proximal and distal ends of the balloon 2 are connected to the outer tube 11 , the outer tube 11 and the inner tube 12 of the catheter body 1 are connected to each other at the farthest end of the balloon catheter, and the outer tube 11 and the inner tube 12 are connected to each other. A liquid-filled cavity is formed between the tubes 12 to provide a passage for the filling liquid.
其中，内管12优选为三层结构，外管11优选为单层结构，内管12由内层高分子、外层高分子以及中间加强层构成，加强层通常为金属丝材缠绕或者编织而成的金属层，外管11由单层高分子层构成。内管12的三层结构保证了导管具有合适的强度和力传导性，导管可以顺利输送，使用过程中不会发生破裂或打折，单层的外管11保证了导管的外径尺寸不会过大，同时也保证了球囊导管的充盈腔的体积足够大。在其他一些实施例中，球囊导管的内管可以为双层结构或四层结构，和/或，球囊导管的外管11可以为双层结构或者三层结构，球囊导管的外管11也可以包含加强层。Among them, the inner tube 12 is preferably a three-layer structure, and the outer tube 11 is preferably a single-layer structure. The inner tube 12 is composed of an inner layer of polymer, an outer layer of polymer, and a middle reinforcing layer. The reinforcing layer is usually made of metal wire winding or braiding. The outer tube 11 is composed of a single polymer layer. The three-layer structure of the inner tube 12 ensures that the conduit has appropriate strength and force conductivity. The conduit can be transported smoothly and will not be broken or discounted during use. The single-layer outer tube 11 ensures that the outer diameter of the conduit will not exceed Large, it also ensures that the filling cavity of the balloon catheter is large enough. In other embodiments, the inner tube of the balloon catheter may have a double-layer structure or a four-layer structure, and/or the outer tube 11 of the balloon catheter may have a double-layer structure or a three-layer structure. 11 Reinforcement layers may also be included.
请进一步参考图1，内管12和/或外管11在与所述球囊2连接的位置对应的材料优选为线性低密度聚乙烯。线性低密度聚乙烯具有高的抗张强度、抗撕裂强度，因此，采用线性低密度聚乙烯与通式a所表示的高分子连接，可以增强导管主体1与球囊2之间的连接强度，连接处不容易断裂，过渡顺滑。Please further refer to FIG. 1 , the material corresponding to the position where the inner tube 12 and/or the outer tube 11 are connected to the balloon 2 is preferably linear low density polyethylene. Linear low-density polyethylene has high tensile strength and tear resistance. Therefore, the connection strength between the catheter body 1 and the balloon 2 can be enhanced by using linear low-density polyethylene to connect with the polymer represented by the general formula a. , the connection is not easy to break and the transition is smooth.
更优的，所述线性低密度聚乙烯经马来酸酐接枝，马来酸酐接枝线性低密度聚乙烯可以进一步提高线性低密度聚乙烯与其他高分子之间的粘接性能，从而提高球囊2与导管主体1的连接强度。例如马来酸酐接枝线性低密度聚乙烯与通式a所表示的高分子材料之间的粘接强度比非马来酸酐接枝的线性低密度聚乙烯与通式a所表示的高分子材料之间的粘接强度更高，使得球囊2与导管主体1的断裂强度更高。More preferably, the linear low-density polyethylene is grafted with maleic anhydride, and the maleic anhydride-grafted linear low-density polyethylene can further improve the bonding performance between the linear low-density polyethylene and other polymers, thereby improving the performance of the ball. The strength of the connection between the balloon 2 and the catheter body 1. For example, the bonding strength between maleic anhydride-grafted linear low-density polyethylene and the polymer material represented by the general formula a is higher than that of non-maleic anhydride-grafted linear low-density polyethylene and the polymer material represented by the general formula a. The bonding strength between them is higher, so that the breaking strength of the balloon 2 and the catheter body 1 is higher.
需要进一步说明的是，本发明提供的球囊材料不限于用于球囊导引导管，还可用于任意需要球囊具有较强顺应性的球囊导管。It should be further explained that the balloon material provided by the present invention is not limited to use in balloon guidance catheters, but can also be used in any balloon catheter that requires strong compliance of the balloon.
【实施例二】[Example 2]
请参考图2，图2为本发明提供的球囊导管的球囊材料的一示例性分子结构式。其中，在实施例二中，R1与R2的结构相同，均为Please refer to Figure 2, which is an exemplary molecular structural formula of the balloon material of the balloon catheter provided by the present invention. Among them, in the second embodiment, the structures of R1 and R2 are the same, both are
图2所表示的高分子中，m取值为5-15，n取值为4-6，x≥1，y≥1，且X：Y≥2:3，X+Y范围为：4-450。In the polymer shown in Figure 2, the value of m is 5-15, the value of n is 4-6, x≥1, y≥1, and X:Y≥2:3, the range of X+Y is: 4- 450.
图2所表示的高分子具有优秀的耐老化性能、高弹性及弹性回复能力，具有更低的永久变形率。The polymer shown in Figure 2 has excellent aging resistance, high elasticity and elastic recovery ability, and has a lower permanent deformation rate.
【实施例三】[Example 3]
请参考图3，图3为本发明提供的球囊导管的球囊材料的一示例性分子结构式。其中，在实施例三中，R1与R2的结构相同，均为Please refer to Figure 3, which is an exemplary molecular structural formula of the balloon material of the balloon catheter provided by the present invention. Among them, in Embodiment 3, R1 and R2 have the same structure, both are
图3所表示的高分子中，m取值为17-28，n取值为2-4，x≥1，y≥1，且X：Y≥2:3，X+Y范围为：4-550。In the polymer shown in Figure 3, the value of m is 17-28, the value of n is 2-4, x≥1, y≥1, and X:Y≥2:3, the range of X+Y is: 4- 550.
图3所表示的高分子更加柔软、其具备高弹性及弹性回复能力。The polymer shown in Figure 3 is softer, has high elasticity and elastic recovery ability.
【实施例四】[Example 4]
请参考图4，本实施例四提供不同材料的拉伸回弹测试的数据，拉伸回弹测试方法为：使用夹具夹持材料的两边并施加拉力，将材料拉伸至100％，随后拉伸至364％，最后拉伸至455％后测试永久变形率。三种材料分别为符合通式a的材料-1、普通TPU-1、硅胶-1。实验结果表明：符合通式a的材料-1具有良好高弹性形变及弹性回复能力，其拉伸后的弹性变形率及永久变形率与硅胶相当，优于普通TPU-1。其中，虽然材料-1的永久变形率略高于硅胶-1，说明使用该材料制备的球囊2的弹性回复能力会略差于使用硅胶-1制备的球囊2，但是82％的永久变形率也能满足球囊导引导管的回抽性能的需求；且由于材料-1可以与其他医用高分子通过热熔焊接工艺粘接，而硅胶材料因其粘接性能差，无法通过通过热熔焊接工艺与其他医用高分子粘接，因此相比于硅胶材料制备的球囊2，采用材料-1制备的球囊2可以避免球囊2与导管主体1连接位置使用胶水，减小了球囊导管的整体外径，且过渡位置外径变化以及力学性能变化平滑，避免了外径变化带来的对血管造成损伤的风险，以及力学性能变化带来的导管弯折或到位困难的风险。Please refer to Figure 4. This Example 4 provides data on the tensile rebound test of different materials. The tensile rebound test method is: use a clamp to clamp both sides of the material and apply tensile force, stretch the material to 100%, and then pull Stretch to 364%, and finally stretch to 455% to test the permanent deformation rate. The three materials are material-1 that conforms to the general formula a, ordinary TPU-1, and silica gel-1. The experimental results show that the material-1 that conforms to the general formula a has good high elastic deformation and elastic recovery capabilities. Its elastic deformation rate and permanent deformation rate after stretching are equivalent to that of silicone and better than ordinary TPU-1. Among them, although the permanent deformation rate of material-1 is slightly higher than that of silica gel-1, indicating that the elastic recovery ability of balloon 2 prepared using this material will be slightly worse than that of balloon 2 prepared using silica gel-1, the permanent deformation of 82% The rate can also meet the demand for retraction performance of the balloon guidance catheter; and because Material-1 can be bonded with other medical polymers through hot melt welding process, silicone material cannot be bonded through hot melt due to its poor bonding performance. The welding process is bonded with other medical polymers. Therefore, compared with the balloon 2 made of silicone material, the balloon 2 made of material-1 can avoid the use of glue at the connection position between the balloon 2 and the catheter body 1, reducing the size of the balloon. The overall outer diameter of the catheter, and the change in outer diameter at the transition position and the change in mechanical properties are smooth, avoiding the risk of damage to blood vessels caused by changes in outer diameter, and the risk of bending or difficulty in placing the catheter due to changes in mechanical properties.
【实施例五】[Example 5]
请参考图5，本实施五提供不同材料的断裂延伸率和200％拉伸变形率下压力值的测试数据。其中，断裂延伸率的测试方法为：使用夹具夹持材料的两边并施加拉力，将材料拉伸直至断裂，记录材料断裂时的延伸率；200％拉伸变形率下压力值的测试方法为：使用夹具夹持材料的两边并施加拉力，将材料拉伸到200％的变形率，记录此时的压力值。测试材料分别为：符合通式a的材料-2、材料-3，硅胶-2、硅胶-3，普通TPU-2、普通TPU-3、普通TPU-4、普通TPU-5、普通TPU-6、普通TPU-7。Please refer to Figure 5. This Implementation 5 provides test data of the elongation at break and the pressure value at 200% tensile deformation rate of different materials. Among them, the test method for elongation at break is: use a clamp to clamp both sides of the material and apply tension, stretch the material until it breaks, and record the elongation when the material breaks; the test method for the pressure value under 200% tensile deformation rate is: Use clamps to clamp both sides of the material and apply tension to stretch the material to a deformation rate of 200%, and record the pressure value at this time. The test materials are: material-2, material-3 that conform to general formula a, silica gel-2, silica gel-3, ordinary TPU-2, ordinary TPU-3, ordinary TPU-4, ordinary TPU-5, ordinary TPU-6 , Ordinary TPU-7.
实验结果表明：符合通式a的材料-2(其硬度为45A)的断裂延伸率为1350％，200％拉伸变形率下压力值为150psi，符合通式a的材料-3(其硬度为55A)的断裂延伸率为950％，200％拉伸变形率下压力值为200psi。相比硅胶-2和硅胶-3，材料-2的断裂延伸率更大，说明材料-2相比硅胶可以承受更大的形变，因此采用材料-2制备的球囊2也可以较好地封堵血管，充盈球囊2时发生断裂失效的概率更小，材料-2在200％拉伸变形率下压力值介于硅胶-2和硅胶-3的压力值之间，说明材料-2充盈时所需要的压力与硅胶相当，充盈时不需要很大的压力；而材料-3的断裂延伸率介于硅胶-2和硅胶-3，说明该材料的拉伸性能也与硅胶相当，满足球囊导引导管封堵血管的需求，材料-3在200％拉伸变形率下压力值略高于硅胶-3，但也满足临床需求。此外，如前文所述，符合通式a的材料-2和材料-3可以与其他医用高分子通过热熔焊接工艺粘接，避免了球囊2与导管主体1连接处使用胶水。综合而言，在充盈能力中，材料-2作为球囊材料相比于硅胶更优，材料-3与硅胶相当，但考虑到粘接性能，材料-2和材料-3相比硅胶都具有更大的优势。The experimental results show that: the elongation at break of material-2 that conforms to the general formula a (its hardness is 45A) is 1350%, and the pressure value under 200% tensile deformation rate is 150 psi. The material-3 that conforms to the general formula a (its hardness is The elongation at break of 55A) is 950%, and the pressure value at 200% tensile deformation is 200 psi. Compared with silica gel-2 and silica gel-3, material-2 has a greater elongation at break, indicating that material-2 can withstand greater deformation than silica gel. Therefore, balloon 2 prepared with material-2 can also be better sealed. Blocking blood vessels, the probability of fracture failure is smaller when balloon 2 is filled. The pressure value of material-2 at 200% tensile deformation rate is between the pressure values of silicone-2 and silicone-3, indicating that when material-2 is filled The required pressure is equivalent to that of silicone, and does not require a lot of pressure during filling; and the elongation at break of material-3 is between silicone-2 and silicone-3, indicating that the tensile properties of this material are also equivalent to silicone, which is satisfactory for balloons. In order to meet the needs of guiding catheters to block blood vessels, the pressure value of Material-3 at 200% tensile deformation rate is slightly higher than that of Silicone-3, but it also meets the clinical needs. In addition, as mentioned above, Material-2 and Material-3 conforming to the general formula a can be bonded with other medical polymers through a hot-melt welding process, avoiding the use of glue at the connection between the balloon 2 and the catheter body 1. Generally speaking, in terms of filling capacity, Material-2 is better than silica gel as a balloon material, and Material-3 is equivalent to silica gel. However, considering the bonding performance, both Material-2 and Material-3 have better filling capacity than silica gel. Big advantage.
对比材料-2和材料-3，球囊2的材料更优选具有45A的硬度。Comparing Material-2 and Material-3, the material of balloon 2 more preferably has a hardness of 45A.
普通TPU-3～普通TPU-7的硬度较大，断裂延伸率过小，且在200％拉伸变形率下压力值都较大，说明这些材料并不适合用于制备球囊2，其在充盈时不能较好贴合血管，破裂风险较大，且充盈所需要的压力大，充盈困难。普通TPU-2虽然硬度合适，在200％拉伸变形率下压力值较小，充盈难度低，但是其断裂延伸率不够，充盈时不能较好贴合血管，破裂风险较大，也不适合作为球囊2的材料。The hardness of ordinary TPU-3 to ordinary TPU-7 is relatively large, the elongation at break is too small, and the pressure value at 200% tensile deformation rate is large, indicating that these materials are not suitable for preparing balloon 2. It cannot fit the blood vessels well during filling, and the risk of rupture is greater, and the pressure required for filling is high, making filling difficult. Although ordinary TPU-2 has suitable hardness, low pressure value at 200% tensile deformation rate, and low filling difficulty, its elongation at break is not enough, and it cannot fit the blood vessels well during filling. The risk of rupture is high, and it is not suitable as a Balloon 2 material.
综上所述，符合通式a的材料-2和材料-3具有适中的硬度(45A和55A)，使其与导管连接处的软硬过渡顺滑，且相比于其他材料具有最高的断裂延伸率，使其在作为球囊2使用的过程中，发生破裂的风险更低；且在充盈时和充盈后，其所需压力较低，与硅胶相当，优于其他普通TPU材料，充盈后对血管壁的压力更小，对血管造成损害的风险更低。To sum up, Material-2 and Material-3 that conform to the general formula a have moderate hardness (45A and 55A), making the transition between soft and hard at the connection with the catheter smooth, and have the highest fracture compared to other materials The elongation rate makes it less likely to rupture when used as a balloon 2; and the pressure required during and after filling is low, which is comparable to silicone and better than other ordinary TPU materials. There is less pressure on the blood vessel walls and a lower risk of damage to the blood vessels.
【实施例六】[Example 6]
请参考图6，图6为球囊2所用材料的硬度对充盈和回抽过程的影响，采用不同硬度的球囊材料和相同的工艺制备了具有不同硬度的球囊导管，通过向球囊2内注射1ml的生理盐水，观察球囊2的膨胀状态，之后，回抽生理盐水，观察球囊2的回抽状态。实验结果表明：球囊材料的硬度为20A与30A的球囊2在充盈过程中发生偏心现象，若在手术过程中，球囊2发生偏心现象，会造成对血管一侧产生的压力过大，可能对血管造成损伤，且无法很好地封堵血管；球囊材料的硬度为62A和80A时，球囊2在充盈过程中发生了偏心或者充盈不充分的现象，且在回抽过程中无法复原，即回抽充盈液后，球囊2无法紧贴导管主体1，若在手术过程中，球囊2无法回抽复原，不方便球囊封堵位置的调整，封堵完成后也会影响球囊导管的回撤；而球囊材料的硬度为40A、45A、55A和60A时，球囊2能正常充盈，充盈时球囊2不发生偏心，回抽时也能恢复球囊2紧贴导管主体1的状态。因此，在本发明中，球囊材料的硬度优选为40A～60A。Please refer to Figure 6. Figure 6 shows the effect of the hardness of the material used in the balloon 2 on the filling and withdrawal process. Balloon catheters with different hardnesses were prepared using balloon materials with different hardness and the same process. By inflating the balloon 2 Inject 1 ml of normal saline, and observe the expansion state of the balloon 2. Then, withdraw the normal saline, and observe the withdrawal state of the balloon 2. The experimental results show that the balloon 2 with a hardness of 20A and 30A will be eccentric during the filling process. If the balloon 2 is eccentric during the operation, it will cause excessive pressure on one side of the blood vessel. It may cause damage to blood vessels and cannot block the blood vessels well; when the hardness of the balloon material is 62A and 80A, the balloon 2 is eccentric or insufficiently filled during the filling process, and cannot be withdrawn during the withdrawal process. Recovery, that is, after withdrawing the filling fluid, the balloon 2 cannot be close to the catheter body 1. If the balloon 2 cannot be withdrawn and recovered during the operation, it will be inconvenient to adjust the balloon sealing position, and it will also affect the Withdrawal of the balloon catheter; when the hardness of the balloon material is 40A, 45A, 55A and 60A, the balloon 2 can be filled normally. The balloon 2 will not be eccentric during filling, and the balloon 2 can be restored to close contact when withdrawing. The status of catheter body 1. Therefore, in the present invention, the hardness of the balloon material is preferably 40A to 60A.
【实施例七】[Example 7]
本实施例提供一种制备前文所述的任意一种球囊导管的方法，包括提供具有通式a所表示的高分子作为球囊材料，并将球囊2与导管主体1之间通过热熔焊接工艺进行连接：This embodiment provides a method for preparing any of the balloon catheters described above, including providing a polymer represented by the general formula a as a balloon material, and thermally melting the balloon 2 with the catheter body 1 Welding process for connection:
其中，R1和R2相互独立选自芳基或带芳基的链段，R3为碳原子数大于等于4的烷基。Among them, R1 and R2 are independently selected from an aryl group or a chain segment with an aryl group, and R3 is an alkyl group with 4 or more carbon atoms.
热熔焊接工艺包括热缩工艺、激光焊接工艺、热焊接工艺等，其中激光焊接工艺具有以下优势：激光束具有很高的能量密度，可以快速加热和熔化材料，从而实现高速、高效的焊接；激光焊接精度高、加热区域小，因此熔深小，焊接速度快，对非焊接区热影响小，非焊接区不会出现热变形的情况；激光焊接可以实现自动化、无人化操作，可以提高生产效率。因此优选激光焊接工艺连接球囊2与导管主体1。Hot melt welding processes include heat shrinking processes, laser welding processes, thermal welding processes, etc. Among them, laser welding processes have the following advantages: the laser beam has a high energy density and can quickly heat and melt materials, thereby achieving high-speed and efficient welding; Laser welding has high precision and small heating area, so the penetration depth is small, the welding speed is fast, the thermal impact on the non-welding area is small, and there will be no thermal deformation in the non-welding area; laser welding can achieve automated and unmanned operation, which can improve Productivity. Therefore, laser welding process is preferred to connect the balloon 2 and the catheter body 1 .
综上所述，本发明提供一种球囊导管，包括：导管主体、球囊，所述球囊套设并连接于导管主体，所述球囊的材料包括通式a所表示的高分子：To sum up, the present invention provides a balloon catheter, which includes: a catheter body and a balloon; the balloon is sleeved and connected to the catheter body; the material of the balloon includes a polymer represented by the general formula a:
其中，R1和R2相互独立选自芳基或带芳基的链段，R3为碳原子数大于等于4的烷基。通过设置球囊的材料，解决了球囊材料不能同时满足力学强度、顺应性和粘接性的要求，以及导管主体和球囊连接处外径偏大的问题，使连接处软硬过渡顺滑，提高球囊导管的到位能力。Among them, R1 and R2 are independently selected from an aryl group or a chain segment with an aryl group, and R3 is an alkyl group with 4 or more carbon atoms. By setting the material of the balloon, it solves the problem that the balloon material cannot meet the requirements of mechanical strength, compliance and adhesiveness at the same time, and the outer diameter of the connection between the catheter body and the balloon is too large, making the transition between soft and hard at the connection smooth. , improve the placement ability of the balloon catheter.
需要说明的是，本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的系统而言，由于与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。It should be noted that each embodiment in this specification is described in a progressive manner, and each embodiment focuses on its differences from other embodiments. The same and similar parts between the various embodiments can be referred to each other. For the system disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple. For relevant details, please refer to the description in the method section.
还需要说明的是，虽然本发明已以较佳实施例披露如上，然而上述实施例并非用以限定本发明。对于任何熟悉本领域的技术人员而言，在不脱离本发明技术方案范围情况下，都可利用上述揭示的技术内容对本发明技术方案作出许多可能的变动和修饰，或修改为等同变化的等效实施例。因此，凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化及修饰，均仍属于本发明技术方案保护的范围。It should also be noted that although the present invention has been disclosed above in preferred embodiments, the above embodiments are not intended to limit the present invention. For any person familiar with the art, without departing from the scope of the technical solution of the present invention, they can use the technical content disclosed above to make many possible changes and modifications to the technical solution of the present invention, or modify it into equivalent changes. Example. Therefore, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of protection of the technical solution of the present invention.
还应当理解的是，除非特别说明或者指出，否则说明书中的术语“第一”、“第二”、“第三”等描述仅仅用于区分说明书中的各个组件、元素、步骤等，而不是用于表示各个组件、元素、步骤之间的逻辑关系或者顺序关系等。It should also be understood that, unless otherwise specified or pointed out, the terms "first", "second", "third" and other descriptions in the specification are only used to distinguish various components, elements, steps, etc. in the specification, rather than Used to express the logical relationship or sequential relationship between various components, elements, steps, etc.
此外还应该认识到，此处描述的术语仅仅用来描述特定实施例，而不是用来限制本发明的范围。必须注意的是，此处的以及所附权利要求中使用的单数形式“一个”和“一种”包括复数基准，除非上下文明确表示相反意思。例如，对“一个步骤”或“一个装置”的引述意味着对一个或多个步骤或装置的引述，并且可能包括次级步骤以及次级装置。应该以最广义的含义来理解使用的所有连词。以及，词语“或”应该被理解为具有逻辑“或”的定义，而不是逻辑“异或”的定义，除非上下文明确表示相反意思。此外，本发明实施例中的方法和/或设备的实现可包括手动、自动或组合地执行所选任务。Furthermore, it should be appreciated that the terminology described herein is used only to describe particular embodiments and is not intended to limit the scope of the invention. It must be noted that, as used herein and in the appended claims, the singular forms "a", "an" and "an" include plural referents unless the context clearly dictates a contrary meaning. For example, a reference to "a step" or "a means" means a reference to one or more steps or means, and may include secondary steps as well as secondary means. All conjunctions used should be understood in their broadest sense. and, the word "or" shall be understood to have the definition of a logical "or" and not the definition of a logical "exclusive-or" unless the context clearly indicates the contrary. Furthermore, implementation of methods and/or devices in embodiments of the present invention may include performing selected tasks manually, automatically, or in combination.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311485461.8ACN117531098A (en) | 2023-11-08 | 2023-11-08 | balloon catheter |
| PCT/CN2024/129628WO2025098280A1 (en) | 2023-11-08 | 2024-11-04 | Balloon catheter |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311485461.8ACN117531098A (en) | 2023-11-08 | 2023-11-08 | balloon catheter |
| Publication Number | Publication Date |
|---|---|
| CN117531098Atrue CN117531098A (en) | 2024-02-09 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311485461.8APendingCN117531098A (en) | 2023-11-08 | 2023-11-08 | balloon catheter |
| Country | Link |
|---|---|
| CN (1) | CN117531098A (en) |
| WO (1) | WO2025098280A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025098280A1 (en)* | 2023-11-08 | 2025-05-15 | 微创神通医疗科技（上海）有限公司 | Balloon catheter |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000051660A1 (en)* | 1999-03-05 | 2000-09-08 | Medtronic, Inc. | Polyurethane balloon catheter |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393858A (en)* | 1990-06-26 | 1995-02-28 | Commonwealth Scientific And Industrial Research Organisation | Polyurethane or polyurethane-urea elastomeric compositions |
| JP3400199B2 (en)* | 1995-08-22 | 2003-04-28 | 住友ベークライト株式会社 | Compliant balloon |
| CN117531097A (en)* | 2023-11-08 | 2024-02-09 | 微创神通医疗科技（上海）有限公司 | balloon catheter |
| CN117531098A (en)* | 2023-11-08 | 2024-02-09 | 微创神通医疗科技（上海）有限公司 | balloon catheter |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000051660A1 (en)* | 1999-03-05 | 2000-09-08 | Medtronic, Inc. | Polyurethane balloon catheter |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025098280A1 (en)* | 2023-11-08 | 2025-05-15 | 微创神通医疗科技（上海）有限公司 | Balloon catheter |
| Publication number | Publication date |
|---|---|
| WO2025098280A1 (en) | 2025-05-15 |
| Publication | Publication Date | Title |
|---|---|---|
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