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Publication numberCN1805718 B
Publication typeGrant
Application numberCN 200480016464
PCT numberPCT/EP2004/006262
Publication dateSep 8, 2010
Filing dateJun 9, 2004
Priority dateJun 13, 2003
Also published asCN1805718A, DE10357742A1
Publication number200480016464.6, CN 1805718 B, CN 1805718B, CN 200480016464, CN-B-1805718, CN1805718 B, CN1805718B, CN200480016464, CN200480016464.6, PCT/2004/6262, PCT/EP/2004/006262, PCT/EP/2004/06262, PCT/EP/4/006262, PCT/EP/4/06262, PCT/EP2004/006262, PCT/EP2004/06262, PCT/EP2004006262, PCT/EP200406262, PCT/EP4/006262, PCT/EP4/06262, PCT/EP4006262, PCT/EP406262
InventorsP西蒙, K克拉茨, A伦德莱因, B施尼特尔
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
CN 1805718 B
The present invention relates to stents for use in the non-vascular and vascular field, which comprise an SMP material.
Claims(22)  translated from Chinese
1. 一种支架,包括形状记忆聚合物材料以用于无血管区或血管区,其中所述形状记忆聚合物材料包括共价聚合物网络。 1. A stent comprising a shape memory polymer material for avascular zone or vessel region, wherein said polymeric material comprises a shape memory polymer network covalently.
2.权利要求I所述的支架,其中所述支架为金属丝线圈设计或开槽管设计或带穿孔的管。 I The stent of claim 1, wherein said stent is a wire coil or slotted tube design or a design with perforated tube.
3.权利要求I所述的支架,其中该支架包括由涂布有形状记忆聚合物材料的材料制成的基本结构。 I The stent of claim 1, wherein the scaffold comprises a basic structure consisting of a shape memory polymer material is coated with the material.
4.权利要求3所述的支架,其中所述形状记忆聚合物材料具有一种或两种记忆形状。 4. The stent according to claim 3, wherein the shape memory polymer material having a shape memory or both.
5.权利要求I或3中所述的支架,进一步包括补充添加剂,所述添加剂选自X射线造影物质和有药效的化合物中的一种或多种。 I stand or in claim 3 wherein, further comprising an additive added, the additive is selected from X-ray contrast substance and has efficacy in one or more of the compounds.
6.权利要求I或3中所述的支架,其中形状记忆聚合物材料选自聚合物网络、热塑性形状记忆聚合物材料、复合材料或上述材料的混合物。 I or holder according to claim 3, wherein the shape memory polymer material is selected from a polymer network, a shape memory polymer mixture of a thermoplastic material, or a composite of these materials.
7.权利要求I或3中所述的支架,其中形状记忆聚合物材料选自具有热诱导形状记忆聚合物效应或光诱导形状记忆聚合物效应的形状记忆聚合物材料。 I or holder according to claim 3, wherein the shape memory polymer material is selected from a shape memory polymer having a thermally induced effect photoinduced shape memory polymer or a shape memory polymer material effect.
8.权利要求I或3所述的支架,其中形状记忆聚合物材料具有生物相容性和/或血液相容性。 I or stent according to claim 3, wherein the shape memory polymer material having a biocompatible and / or blood compatibility.
9.权利要求I或3中所述的支架,其中形状记忆聚合物材料的e-模量为O. 5至50MPa。 I stand or in claim 3 wherein, wherein the shape memory polymer e- modulus material is O. 5 to 50MPa.
10.权利要求I或3所述的支架,其中形状记忆聚合物材料的断裂伸长率为100至1200%。 I or stent according to claim 3, wherein the shape memory polymer material elongation at break of 100 to 1200%.
11.权利要求I或3所述的支架,其中形状记忆聚合物材料的回复固定率高于90%。 I or stent according to claim 3, wherein the shape memory polymer material is higher than 90% of the responses is fixed.
12.权利要求11所述的支架,其中形状记忆聚合物材料的回复固定率高于92%。 12. A bracket according to claim 11, wherein the shape memory polymer material is higher than 92% of the responses is fixed.
13.权利要求11所述的支架,其中形状记忆聚合物材料的回复固定率高于95%。 13. A bracket according to claim 11, wherein the shape memory polymer material is fixed response greater than 95%.
14.权利要求11所述的支架,其中形状记忆聚合物材料的回复固定率高于98%。 14. A bracket according to claim 11, wherein the shape memory polymer material is higher than 98% of the responses is fixed.
15.权利要求I或3所述的支架,其中形状记忆聚合物材料重复进行五次热-机械实验后的回复率高于90%。 I or scaffold of claim 3, wherein, wherein the shape memory polymer material is repeated five times the thermal - mechanical response rate of 90% after the experiment.
16.权利要求15所述的支架,其中形状记忆聚合物材料重复进行五次热-机械实验后的回复率高于92%。 16. A bracket according to claim 15, wherein the shape memory polymer material is repeated five times the thermal - mechanical recovery rate after the experiment in 92%.
17.权利要求15所述的支架,其中形状记忆聚合物材料重复进行五次热-机械实验后的回复率高于95%。 17. A bracket according to claim 15, wherein the shape memory polymer material is repeated five times the thermal - mechanical response rate of 95% after the experiment.
18.权利要求15所述的支架,其中形状记忆聚合物材料重复进行五次热-机械实验后的回复率高于98%。 18. A bracket according to claim 15, wherein the shape memory polymer material is repeated five times the thermal - mechanical recovery rate after the experiment in 98%.
19.权利要求7所述的支架,其中网络包括己内酯单元、十五内酯单元、乙二醇单元、丙二醇单元、乳酸单元和/或乙醇酸单元。 19. A bracket according to claim 7, wherein the network comprises means caprolactone, pentadecalactone units, ethylene unit, propylene unit, lactic acid unit and / or glycolic acid units.
20.权利要求I或3所述的支架,其中网络由交联的己内酯大分子单体组成。 I or 3, wherein the bracket 20. The claim, wherein the cross-linked network of caprolactone macromer composition.
21.制备前述权利要求中任一项所述的支架的方法,包括使大分子单体发生交联反应而形成所述支架的永久形状。 21. A method for preparing of the preceding claims scaffold according to any one of a macromer comprising crosslinking reaction to form the permanent shape of the stent.
22. —种成套工具,包括权利要求I至20中任一项所述的支架,还包括球囊导管。 22. - kind of kit, including the claims I to stand in any one of claims 20, further comprising a balloon catheter.
Description  translated from Chinese
支架 Support

技术领域 Technical Field

[0001] 本发明的主题是一种由形状记忆聚合物(SMP)制成的用于无血管区(non-vascular field)或血管区(vascular field)的临时性支架。 [0001] A subject of the invention is made of a shape memory polymer (SMP) for the avascular zone formed (non-vascular field) or vascular regions (vascular field) temporary stent. 所述支架可以通过形状记忆效应最小化,并且可通过微创外科手术(minimally invasive surgery)移除。 The stent may be minimized by the shape memory effect, and may be removed by minimally invasive surgery (minimally invasive surgery). 本发明的另一个主题是所述支架的植入和移除、以及制造和编程(program)方法。 Another subject of the invention is that the stent implantation and removal, and build and program (program) method.

背景技术 Background

[0002] 为治疗管堵塞或管状器官收缩或在外科手术后,将管状组织支撑物(支架)置入管状器官内。 [0002] for the treatment of pipe blockage or tubular organ contraction or after the surgery, the tubular tissue supports (stents) into the tubular organ. 所述支撑物用于使收缩部位保持开放或者取代受伤管状器官的作用以恢复体液的正常通过或排出。 The support for the shrinkage site to remain open or replace injured tubular organ through action to restore normal body fluids or discharge. 支架也可置入血管内以治疗血管堵塞或收缩,所述支架使收缩部位保持开放并恢复血液的正常流动。 Intravascular stent may be placed in the treatment of vascular blockage or contraction, the shrinkage of the stent to keep the site open and restore normal blood flow.

[0003] 支架通常为由一种金属丝网制成的圆柱形结构(金属丝线圈设计),或者可为穿孔管或非穿孔管(开槽管设计)。 [0003] Stents are typically made by metal mesh cylindrical structure (wire coil design) or a perforated pipe or perforated pipe (slotted tube design). 常规支架的长度为Icm和12cm,直径可以是I至12mm。 The length of a conventional stent is Icm and 12cm, diameter may be I to 12mm.

[0004] 在支架的机械性能要求方面存在矛盾。 [0004] there is a contradiction in terms of mechanical performance requirements of scaffolds. 一方面,支架必须对被支撑的管状器官施加较大的径向力。 On the one hand, the bracket must be greater radial force is applied to the tubular organ to be supported. 另一方面又要求支架可径向压缩,从而能够轻松地将其置入管状器官内,而不损伤管壁或者外围组织。 On the other hand requires the stent can be radially compressed, which can easily be inserted into a tubular organ without damaging the wall or the surrounding tissue.

[0005] 上述问题的解决是通过将支架以压缩形式置入,并仅在到达正确位置后安装。 [0005] The above problem is solved by the stent into a compressed form, and in the correct position after installation only. 压缩状态下的直径小于扩张状态的直径。 Compression diameter smaller than the diameter of the expanded state state. 该方法基本上也可用于支架的微创移除。 The method can also be used minimally invasive removal of substantially bracket. 但可能存在的问题是,通常使用的金属材料并不总是完全地规则扩张,而且无法再次折叠,这样有可能会损伤边缘组织(bordering tissue)。 But there may be a problem that the metal material is usually used is not always completely rule expansion, and not collapse again, this may damage the edge of the tissue (bordering tissue).

[0006] 对于支架的微创置入而言,已经建立了两种不同的技术(市场报告“USperipheral and vascular stent and AAA stent graft market,,(Frost & Sullivan),2001): [0006] For the purposes of minimally invasive stent placement, we have established two different techniques (Market Report "USperipheral and vascular stent and AAA stent graft market ,, (Frost & Sullivan), 2001):

[0007]-球囊扩张支架(体系由球囊、导管、支架组成) [0007] - balloon expandable stents (system composed of balloon catheters, stents composition)

[0008]-自扩张支架(体系由置入套管(防护套(sheeth))、导管、支架组成); [0008] - self-expanding stents (system composed into the sleeve (protective sleeve (sheeth)), catheters, stents composition);

[0009]自扩张支架由形状记忆材料(SM材料)组成,其中最早出现的是金属SM材料,例如镍钛金属互化物(nitinol)。 [0009] The self-expanding stent made of a shape memory material (SM material), of which first appeared in the SM metallic material, such as nickel-titanium intermetallic compound (nitinol). 形状记忆效应是一种近年来广泛关注研究的效应,通过施加外界刺激该效应可使形状发生想要的改变(这一方面的相关具体内容,可参考公开文献,例如“Shape Memory Alloys”, Scientific American,第281 卷(1979),第74 至82 页)。 Shape memory effect is a widespread concern in recent years, the effect study the effect by applying external stimuli can happen desired shape changes (relevant details in this regard, reference publications, such as "Shape Memory Alloys", Scientific American, Vol. 281 (1979), pp. 74 to 82). 所述材料能够在温度升高的情况下特定地改变其形状。 The material can be at elevated temperatures of a specific change its shape. 形状记忆效应被激活以“自动”增大支架的直径,并将其固定在使用位置处。 Shape memory effect is activated to "automatic" increase the diameter of the stent, and fixed in position of use.

[0010] 如上所述,扩张支架的移除是一个难题。 [0010] As described above, the expansion of the stent is removed is a problem. 如果必须将支架从管腔内拔出,则有可能由于摩擦而损伤外围组织,因为支架太大并且具有锋利的边缘。 If you must pull out from inside the stent lumen, it is possible to damage the surrounding tissue due to friction, because the stent is too large and has sharp edges. 因此,如果必须将支架再次移除,也可将形状记忆效应用于减小支架的直径。 Therefore, if you must remove the stand again, the shape memory effect can also be used to reduce the diameter of the stent. 由形状记忆金属制成的可移除式植入体(支架)的实例从现有技术中已知:US 6413273 “Method and system fortemporarilysupporting a tubular organ” ;US 6348067 “Methodand system with shape memoryheating apparatus for temporarilysupporting a tubular organ,,,US 5037427“Methodof implantinga stent within a tubular organ of a living body and removingsame,,;US 5197978 “Removable heat-recoverable tissue supportingdevice,,。 Examples of removable implant made of a shape memory metal (bracket) is known from the prior art: US 6413273 "Method and system fortemporarilysupporting a tubular organ"; US 6348067 "Methodand system with shape memoryheating apparatus for temporarilysupporting a tubular organ ,,, US 5037427 "Methodof implantinga stent within a tubular organ of a living body and removingsame ,,; US 5197978" Removable heat-recoverable tissue supportingdevice ,,.

[0011] 在对镍敏感的情况下不能使用镍钛金属互化物。 [0011] In the case of nickel-sensitive can not use nickel-titanium intermetallic compound. 这种材料亦非常昂贵,而且只能通过繁复的方法进行编程。 This material is also very expensive, and can be programmed only by complicated methods. 这种编程方法需要相对较高的温度,因此在体内进行编程是不可能的。 This programming method requires relatively high temperatures, and therefore in vivo, programming is not possible. 所以SM材料在体外进行编程,也就是说使其成为临时的形状。 SM material is therefore programmed in vitro, that is to become a temporary shape. 植入后,形状记忆效应被激活并且支架扩张,即恢复为永久的形状。 After implantation, the shape memory effect is activated and the stent is expanded, the permanent shape is restored. 这样就不可能再次利用形状记忆效应将支架移除。 This makes it impossible to reuse the shape memory effect will stand removed. 金属支架中一个不仅仅发生在血管区的常见问题首先是再狭窄(restenosis)的发生。 Metal stents in a common problem not only in the area of the first vessel restenosis (restenosis) occurs.

[0012] 另一方面,虽然由其它SM材料制成的金属支架(例如US 5197978中所述)能够利用形状记忆效应将支架移除。 [0012] On the other hand, although the other SM material metal stents (such as described in US 5197978) to take advantage of the shape memory effect of the stent removed. 但是,这种金属材料的制造非常繁复,组织的相容性也不是总能保证。 However, the manufacture of the metal material is very complicated, histocompatibility is not always guaranteed. 由于支架的机械性能适应性不够,炎症和疼痛经常会发生。 Because of the mechanical properties of the stent adaptability enough, inflammation and pain often occur.

[0013] US 5716410“Temporary stent and method of use”中所述的临时性支架是一种由形状记忆塑性材料制成的线圈。 [0013] US 5716410 "Temporary stent and method of use" of the coil is a temporary stent from a shape memory plastic material. SMP材料中带有加热金属丝。 Heating wire materials with SMP. 加热金属丝通过导管轴与电子控制器相连,其中,轴的末端为一根空管,并套在线圈端的上面。 Heating wire is connected to the catheter shaft by an electronic controller, wherein one end of the shaft for air traffic control, and set on top of the coil end. 如果将临时扩张形状的植入支架加热至高于转换温度(switching temperature) Ttrans,线圈的直径将减小。 If the temporary expansion of the shape of a stent is heated to a temperature above the transition temperature (switching temperature) Ttrans, the coil diameter will be reduced. 这样就能够很容易地移除支架。 This makes it possible to easily remove the stent. 线圈结构的缺点在于径向力太小以至于无法扩张管腔。 Drawback is that the radial force coil structure is too small to expand the lumen. 线圈的径向力仅分布在与组织的小范围接触面上。 Radial force of the coil is distributed only in a small area in contact with the tissue surface. 甚至存在有局部机械负荷过重的危险,这可能是由于切入组织所产生的压力引起的。 There is even the danger of local mechanical overload, which may be cut into the tissue due to the pressure generated by the induced. 而且已经证实,将导管轴(加热元件)连接到植入线圈的加热金属丝上是比较困难的,因为必须把导管轴套在线圈的一端上。 And it has confirmed that the catheter shaft (heating element) is connected to the heating wire coil implant is more difficult, because of the need to catheter sleeve at the upper end of the coil.

[0014] 现有技术的另一个实例涉及形状记忆聚合物支架,该支架可以临时的压缩形状植入,其中所需要的永久尺寸通过形状记忆效应在使用位置处形成(s 4950285,US 6245103,US 6569191,EP 1033145)。 Another example of [0014] the prior art relates to a shape memory polymer scaffold, the scaffold can be implanted temporarily compressed shape, wherein the permanent size required by the shape memory effect is formed at a position of use (s 4950285, US 6245103, US 6569191, EP 1033145). 支架的移除可以通过其它外科手术或者通过体内的材料吸收实现。 Removing the stand can be achieved by other surgical or absorbed by the body of material to achieve. 所使用材料的缺点在于其吸收时的脆化以及颗粒物的产生,而产生的颗粒物在从装置释放时可能引起堵塞。 The disadvantage of using the material in its embrittlement and particle generation absorbed, and particulate matter generated may cause blockage upon release from the device. 而且,吸收也可能改变植入体的结构/性质,从而导致与血液和/或组织不相容。 Furthermore, the absorption may change the structure of the implant / properties, resulting in incompatibility with blood and / or tissues.

[0015] 另一个经常出现的问题是由于支架对外围组织的机械适应性不够而引起的疼痛以及支架的移位。 [0015] Another recurring problem is due to stand against the surrounding tissue caused by inadequate mechanical adaptability pain and stent displacement.

[0016] 发明目的 [0016] invention purpose

[0017] 由于支架在医学上的使用越来越广泛,上述缺点必须努力加以克服。 [0017] Since the stent in medicine more widely used, efforts must be made to overcome the above drawbacks. 因此,需要可实现微创植入并能平稳移除的用于无血管区或血管区的支架。 Therefore, minimally invasive and can be achieved smoothly removed for stents avascular zone or vascular region. 支架的材料首先应适用于相应的使用位置,例如考虑不定机械载荷。 Scaffolds should first apply to the appropriate use of location, such as mechanical loads considered uncertain. 所述材料应优选使支架能进一步官能化(functionalization),例如通过包埋其他可医用的物质。 The material should preferably stent can be further functionalized (functionalization), for example, by embedding other medical substances.

[0018] 为克服现有技术的缺点,需要有: [0018] to overcome the disadvantages of the prior art, the need for:

[0019]- 一种可实现支架微创植入及移除的简易方法, [0019] - A simple method to achieve minimally invasive stent implantation and removal,

[0020]- 一种可微创且无损伤移除的支架,优选通过利用形状记忆效应, [0020] - a minimally invasive and can be removed without damage to the frame, preferably by using shape memory effect,

[0021]- 一种在血管应用或非血管应用情况下不长入管壁的支架, [0021] - an application in vascular or nonvascular application is not long into the wall bracket,

[0022]- 一种表面具有血液相容性(haemocompatible)的支架, [0022] - A surface having blood compatibility (haemocompatible) of the stent,

[0023]- 一种使用时具有足够的机械强度/牢固性的支架,以在即使可能发生生物降解的情况下,其功能也不受影响, [0023] - having a sufficient mechanical strength / robustness when a stent used to occur even in the case of biodegradation, its function is not affected,

[0024]- 一种不与被支撑的组织一同生长从而可简单移除的支架,而且所述支架还能够抑制生物膜的形成或者微生物的包囊作用(encapsulation), [0024] - a non-supported organization and thus can be easily removed with the growth of the bracket, and the bracket can also inhibit the formation of biofilms or microbial encapsulation (encapsulation),

[0025]- 一种制造这种支架并对其进行编程的方法。 [0025] - A method of programming their manufacture and this bracket.


[0026] 该目的可通过如权利要求中所定义的本发明主题来解决。 [0026] This object can be solved by the present invention as claimed subject matter as defined. 这种支架包括一种形状记忆材料(SMP材料),优选表现出热诱导或者光诱导形状记忆效应的SMP材料。 This stent comprises a shape memory material (SMP material), preferably exhibit thermally induced or photo-induced shape-memory effect SMP material. 本发明所使用的SMP材料可以记忆一种或两种形状。 SMP material of the present invention can be used in one or both of the shape memory.

[0027] 此类支架全部或至少部分地解决了上述问题。 [0027] Such stents whole or at least partially solve the above problems. 因此,本发明提供了一种包括SMP材料的支架,所述支架可以利用形状记忆效应微创且无损伤地使用,该支架具有组织相容性并且具有足够的强度/稳定性,从而可在所需使用时间后移除,在此期间所述支架发挥其作用而不损失机械稳定性。 Accordingly, the present invention provides a stent comprising a stent SMP material can shape memory effect and no damage invasive use, the stent has a histocompatibility and has a sufficient strength / stability, so that in the After the time required to remove, during which the bracket to play its role without loss of mechanical stability.

[0028] 特别地,为防止生物膜的产生及支架的长入,可针对非血管应用改进支架,包括:适当选择SMP材料片段,表面改性、特别是微结构处理(micro-structuring),或者适当涂层,或者使用植入后可由支架释放出来的消毒物质。 [0028] In particular, in order to prevent biofilm production and stent ingrowth can be improved stents for non-vascular applications, including: SMP material appropriately selected fragments, surface modification, especially micro structure processing (micro-structuring), or appropriate coating, or by using implants after stent out disinfection substances.

[0029] 而且,所述支架还可根据使用位置进行适当的改进使其适应各种要求,因为针对例如不同的PH值条件、特异性酶的存在、或一般的微生物环境可能会有特殊要求。 [0029] Further, the stent may be used according to suitable modifications to adapt the position of the various requirements, for example because of different conditions PH value, the presence of the specific enzyme, or the general environment of the microorganisms may be special requirements. 通过分别选择SMP材料的片段,可将这些要求考虑进来。 Were selected by fragment SMP material, these requirements can be taken into account.

附图说明 Brief Description

[0030] 图I示意性示出本发明支架的永久形状及临时形状的尺寸区别。 [0030] FIG. I schematically shows the size difference between permanent and temporary shape of the shape of the present invention stent.

[0031] 图2示出置入及移除支架的操作步骤示意图。 [0031] FIG. 2 shows the procedure to remove the stent implantation and schematic. 浅灰色部分表示支架,深灰色部分表示导管球囊,黑色部分表示导管。 Light gray represent bracket, dark gray in the catheter balloon catheter black part represents.

[0032] 图3示意性示出具有两种记忆形状的支架的作用原理。 [0032] Figure 3 schematically illustrates the principle of having a role in both the shape memory stent.


[0033] 在一个优选实施方案中,所述目的通过SMP支架解决,其特征在于: [0033] In a preferred embodiment, the object is achieved by solving SMP stent, comprising:

[0034]-永久形状的支架预先安装在温控球囊导管或者带有适合光源(优选UV)的球囊导管上, [0034] - permanent shape of the stent pre-mounted on a balloon catheter or the thermostat with a balloon catheter suitable light source (preferably UV), and

[0035]-临时形状的直径大于永久形状的直径(参考图I), [0035] - temporary shape of diameter greater than the diameter of the permanent shape (see Fig. I),

[0036]-临时形状用作组织支撑物, [0036] - temporary shape as a tissue support,

[0037] -SMP的转换温度为40C或更高,转换波长(switchingwavelength)为260nm或更长, [0037] -SMP convert 40 C for temperature or higher, wavelength conversion (switchingwavelength) of 260nm or longer,

[0038]-植入的支架由于SM效应变为永久的压缩形状,从而可易于通过微创外科手术移除。 [0038] - the implanted stent into a permanent effect due to the SM compact configuration, which can be easily removed by minimally invasive surgery.

[0039] 一种微创置入并移除支架的可行方法,包括以下步骤(图2): [0039] A possible method of minimally invasive implantation and removal of the stent, comprising the steps of (Figure 2):

[0040]置入: [0040] placement:

[0041] I.将预先安装在温控球囊导管或带有适合光源的球囊导管上的支架以微创方式置入管状无血管器官内, [0041] I. will be pre-installed in a temperature-controlled balloon catheter or stent suitable light source with a balloon catheter inserted in a minimally invasive manner without vascular tubular organ,

[0042] 2.可以通过导管将放置的支架加热至高于其Trans (至少40C )(球囊充满温水或暖气), [0042] 2. You can place the stent through the catheter is heated above its Trans (at least 40 C) (balloon filled with warm water or heating).

[0043] 3.通过以下方法使支架成为临时的形状(扩张),即进一步将温水或暖气注入球囊导管直至达到所需要的形状/扩张,也就是说仅在植入位置处直接对支架进行编程。 [0043] 3. The following method allows the stent to become temporary shape (expansion), that further injection of hot water or heating the balloon catheter until it reaches the desired shape / expansion, which means that only the direct stent implantation at the location programming.

[0044] 4.通过导管将扩张的支架冷却至低于Ttrans (球囊充满冷水或冷气)或者用波长大于260nm的光照射以固定临时形状, [0044] The catheter will expand by rack to cool to below Ttrans (balloon filled with cold water or air conditioning) or light with wavelengths longer than 260nm is irradiated to fix the temporary shape,

[0045] 5.收缩球囊和/或停止照射,将球囊导管移除。 [0045] 5. shrink the balloon and / or stop the irradiation, the balloon catheter is removed.

[0046]移除: [0046] Remove:

[0047] I.为进行移除,将球囊导管置入支架部分, [0047] I. For the removal of the balloon catheter stent section,

[0048] 2.用液体(水)或气体扩张球囊以与支架直接接触并且保证传热或光照射, [0048] 2. The liquid (water) or a gas balloon to expand the stent and in direct contact with the heat or light irradiation to ensure,

[0049] 3.通过导管将支架加热至高于Ttrans或用波长小于260nm的光照射以激活形状记忆效应,使支架恢复为永久(较小的)形状, [0049] 3. The stent through the catheter is heated to a temperature above Ttrans or irradiated with light with a wavelength less than 260nm to activate the shape memory effect, so that the bracket back to the permanent (smaller) shape,

[0050] 4.缓慢释放球囊(排出液体(水)或气体),其中支架收缩(SM效应)并自动将其本身固定至球囊上, [0050] The slow release of the balloon (discharge of liquid (water) or a gas), wherein the bracket shrinkage (SM effect) and automatically secured to the balloon itself,

[0051] 5.可以将压缩支架冷却,并与球囊导管一并移除。 [0051] 5. You can compress rack to cool and remove together with the balloon catheter.

[0052] 或者,这种方法也可如下所述: [0052] Alternatively, this method can be described as follows:

[0053]置入: [0053] placement:

[0054] I.将预先安装在温控球囊导管上的支架通过微创外科手术的方法置入管状器官内, [0054] I. will be pre-installed on the temperature of the stent balloon catheter through minimally invasive surgical approach within the tubular organ,

[0055] 6.通过导管将放置的支架加热至高于其Ttrans(至少40C )(球囊充满温水或暖气), [0055] 6. catheter stent placement heated above its Ttrans (at least 40 C) (balloon filled with warm water or heating).

[0056] 7.通过以下方法使支架成为临时的形状(扩张),即进一步将温水或暖气注入球囊导管直至达到所需要的形状/扩张;也就是说在植入位置处直接对支架进行编程, [0056] 7. The method by the stent to become temporary shape (expansion), that further injection of hot water or heating the balloon catheter until it reaches the desired shape / expansion; that is implanted in a position to stand directly program ,

[0057] 8.通过导管将扩张的支架冷却至低于Ttans (球囊充满冷水或冷气)以固定临时形状, [0057] 8. The catheter will expand by rack to cool to below Ttans (balloon filled with cold water or cooling) to secure the temporary shape,

[0058] 9.收缩球囊,将球囊导管移除。 [0058] 9. shrink the balloon, the balloon catheter is removed.

[0059]移除: [0059] Remove:

[0060] 10.为进行移除,将球囊导管置入支架部分, [0060] 10. In order to be removed, the balloon catheter stent section,

[0061] 11.用液体(水)或气体扩张球囊以与支架直接接触并且保证传热, [0061] 11. The liquid (water) or a gas balloon to expand the stent and in direct contact with the heat transfer assurance,

[0062] 12.通过导管将支架加热至高于Ttans (球囊充满温水或暖气)以激活形状记忆效应,使支架恢复为永久(较小的)形状, [0062] 12. A stent through the catheter is heated to a temperature above Ttans (balloon filled with warm water or heating) to activate the shape memory effect, so that the bracket back to the permanent (smaller) shape,

[0063] 13.缓慢释放球囊(排出液体(水)或气体),其中支架收缩(SM效应)并自动将其本身固定至球囊上, [0063] 13. The balloon slowly released (discharged liquid (water) or a gas), wherein the bracket shrinkage (SM effect) and automatically secured to the balloon itself,

[0064] 14.可以将压缩支架冷却,并与球囊导管一并移除。 [0064] 14. A stent can be compressed cooled and removed together with the balloon catheter.

[0065] 一种微创置入并移除具有光诱导形状记忆的支架的可行方法包括以下步骤(图2): [0065] A minimally invasive insertion and removal feasible method photoinduced shape memory stent comprising the steps of (Figure 2):

[0066]置入: [0066] placement:

[0067] I.将预先安装在带有适合光源的球囊导管上的支架通过微创外科手术方法置入管状器官内, [0067] I. will be pre-installed on a balloon catheter with a suitable light source stent minimally invasive surgical procedures within the tubular organ,

[0068] 2.通过以下方法使支架成为临时的形状(扩张),即进一步将(温)水或(暖)气体注入球囊导管直至达到所需要的形状/扩张;也就是说在植入位置处直接对支架进行编程。 [0068] 2. The method of the stent by becoming a temporary shape (expansion), that further (warm) water or (heating) gas injected into the balloon catheter until the desired shape / expansion; that at the site of implantation It can be programmed directly at the stent.

[0069] 3.用波长大于260nm的光照射扩张的支架以固定临时形状, [0069] 3. irradiated with light with a wavelength greater than 260nm expandable stent to fix the temporary shape,

[0070] 4.收缩球囊和/或停止照射,将球囊导管移除。 [0070] The shrink the balloon and / or stop the irradiation, the balloon catheter is removed.

[0071]移除: [0071] Remove:

[0072] 5.为进行移除,将球囊导管置入支架部分, [0072] 5. For the removal of the balloon catheter stent section,

[0073] 6.用液体(水)或气体扩张球囊以与支架直接接触并且保证光照射, [0073] 6. The liquid (water) or a gas in direct contact with the balloon dilatation and stent guaranteed photoirradiation,

[0074] 7.用波长小于260nm的光照射支架以激活形状记忆效应,使支架恢复为永久(较小的)形状, [0074] 7. wavelength less than 260nm light irradiation stent to activate the shape memory effect, so that the bracket back to the permanent (smaller) shape,

[0075] 8.缓慢释放球囊(排出液体(水)或气体),其中支架收缩(SM效应)并自动将其本身固定至球囊上, [0075] 8. The balloon slowly released (discharged liquid (water) or a gas), wherein the bracket shrinkage (SM effect) and automatically secured to the balloon itself,

[0076] 9.将压缩支架与球囊导管一并移除。 [0076] 9. The compressed stent and balloon catheter will be removed.

[0077] 对于仅在使用位置处进行编程的支架,由于其仅在该位置变为临时形状,因此就这一方面而言,如果支架在置入体内前于体外加热至高于转变温度将是特别优选的。 [0077] For use only in programming position stand, because it is only in this position to the temporary shape, and therefore this aspect is concerned, if the stent before implantation in vivo in vitro heated to above the transition temperature will be of particular It preferred. 由于此时力并没有作用于支架,因此支架的扩张未发生改变。 Since this time the force does not act on the stent, thus expanding stents not changed. 但是,这种加热会使得支架的SMP材料变得柔软而有弹性。 However, this heat will make the bracket SMP material becomes soft and flexible. 与加热前非常刚硬的支架相比,预加热的支架可以通过这种方式更好地、也更容易地置入。 Compared with the previous heating very rigid frame, pre-heating of the stent may be better and more easily placed in this way. 特别是使用大型支架和/或必须使支架通过重伤的管等情况时,这种预加热的方法在支架置入方面具有显著的改善。 Particularly the use and / or serious injury must stand through a tube, etc., such pre-heating method in terms of stenting significantly improved large bracket.

[0078] 在置有支架的多种应用中,将支架的实际位置与所需的使用位置准确对应是非常重要的。 [0078] In the set with a bracket of a variety of applications, the actual position of the stand and the exact location corresponding to the desired use is very important. 如果连续置入两个支架,则这一点尤其重要,因为精确的放置对于确保想要的成功尤其重要。 If two consecutive stent placement, this is especially important, because accurate placement is especially important to ensure the desired success. 然而,就常规支架而言,很难对支架的放置进行校正,因为难以解决支架在使用位置处的再次折叠。 However, conventional stents, it is difficult to correct placement of the stent, the stent is difficult to solve because the use of re-folded position. 而本发明的支架仅在使用位置处直接进行编程,因此具有显著优势。 The stent of the present invention only be programmed using the position directly, and therefore has a significant advantage. 由于本发明的支架在该实施方案中的扩张状态为临时形态,因此可通过激活SM效应简单地实现支架缩小,从而可以将再次缩小的支架再次放置,实现放置的简易校正。 Due to the expansion of state support of the invention in this embodiment as a temporary form, it can be simply achieved by activating the SM effect narrow stand, which can be re-narrowing of stent placement once again, to achieve a simple correction of placement. 在校正之后,可通过上述方法步骤对本发明的支架再次重新进行编程,使其作为组织支撑物的临时形态存在。 After the correction, by the above method steps of the inventive stent reprogrammed again, to act as a temporary form of organizational support exists.

[0079] 校正置入可概括为以下方法步骤: [0079] correction can be summarized into the following process steps:

[0080] I.将预先安装在温控球囊导管上的支架置入管状器官内。 Bracket [0080] I. The pre-installed on the thermostat inside the balloon catheter into the tubular organ.

[0081] 2.通过导管将放置的支架加热至高于转变温度。 [0081] 2. Place the stent through the catheter is heated to above the transition temperature.

[0082] 3.使支架成为临时的形状(扩张的)直至其达到所需要的形状(扩张)。 [0082] 3. The stent become temporary shape (expanded) until it reaches the desired shape (expansion).

[0083] 4.通过导管将扩张的支架冷却至低于转变温度以固定临时状态。 [0083] The catheter will expand by rack to cool to below the transition temperature to secure a temporary state.

[0084] 上述步骤完成后,如果检测到支架仍然没有正确放置,还可进行以下校正步骤: [0084] After the above steps are completed, if the stent is still not detected properly placed, but also for the following correction step:

[0085] 5.通过导管将支架加热至高于转变温度,以激活形状记忆效应并将支架恢复为较小的形状。 [0085] 5. The stent catheter is heated to above the transition temperature, to activate the shape memory effect and to restore the stent to a smaller shape.

[0086] 6.缓慢释放球囊,其中支架收缩。 [0086] 6. The slow release of the balloon, wherein the stent contraction.

[0087] 7.位于球囊上的支架就可以正确放置。 [0087] 7. Located on the balloon stent can be placed properly.

[0088] 随后重复步骤3和4,将支架重新放置。 [0088] and then repeat steps 3 and 4, reposition the stent. 然后移除导管。 Then remove the catheter.

[0089] 对于表现出光诱导形状记忆效应的形状记忆材料而言,当然也可以以类似方法实施此处所述的校正过程。 [0089] For the exhibit light-induced shape-memory effect of shape memory material, of course, in a similar manner as described herein correction process.

[0090] 具有两种记忆形状的支架 [0090] The bracket has two memory shape

[0091] 进行两次编程的支架具有以下优点:该支架可以首先以压缩形式通过微创外科手术植入,并通过加热将其固定于使用位置处。 [0091] programmed twice stent has the following advantages: First, the stent may be compressed to form implanted by minimally invasive surgery, and will be fixed in position by the use of heat. 发生初次形变(例如直径增大)。 Initial deformation occurs (such as diameter increases). 在使用位置处经过所需要的停留时间之后,再次加热支架以引起二次形变(例如直径减小),从而可通过微创外科手术的方法将支架移除。 After using the position required residence time, the stent is heated again to cause the secondary deformation (e.g., reduced diameter), so that by the method of minimally invasive surgery to remove the stent.

[0092] 具有两种记忆形状的支架可以由具有以下特征的SMP制成:所述SMP具有共价网络结点(net point)及两个转换段(switching segment)或两个形变温度(transitionaltemperature) Ttrans,其中采用TtamsI < TtMns2,并且两个转换温度均高于体温。 [0092] The bracket has two memory shape by the SMP may be made with the following characteristics: the SMP having covalently network nodes (net point) and the two switching segments (switching segment) or two deformation temperature (transitionaltemperature) Ttrans, where the use of TtamsI <TtMns2, and two transition temperature is higher than body temperature. 共价网络结点决定支架的永久形状,各转换段决定临时形状。 Covalent network node determines the permanent shape of the stent, each switching segments form temporary decision.

[0093] 在一个实施方案中,管状支架的特征在于永久形状的直径Dpmi较小,第一临时形状的直径DtempI大于Dperm,第二临时形状的直径Dtemp2小于DtempI =Dperm < DtempI > Dtemp2。 [0093] In one embodiment, the stent characterized in that the diameter of the tubular-shaped permanent Dpmi smaller diameter than the shape of the first temporary DtempI Dperm, Dtemp2 diameter smaller than the second temporary shape DtempI = Dperm <DtempI> Dtemp2.

[0094] 第二临时形状的直径可以与永久形状的直径相同或不同:DpOT = Dtemp2或 [0094] diameter of the second temporary shape may be the same or different diameters permanent shape: DpOT = Dtemp2 or

Dperm ^ ^temp^ ◦ Dperm ^ ^ temp ^ ◦

[0095] 支架的双编程由以下方法步骤构成: [0095] bracket dual programming by the following method steps constitute:

[0096] I.将支架加热至高于Ttrans2, [0096] I. The stent is heated to above Ttrans2,

[0097] 2.在低于TtMns2且高于TtransI的温度下扩张支架 Expandable stent [0097] 2. below TtMns2 temperatures and higher than TtransI

[0098] 3.将支架冷却至低于Ttrans2且高于TtransI的温度, [0098] 3. The stent is cooled to below and above TtransI Ttrans2 temperature,

[0099] 4.将支架压缩为DtempI, [0099] The compression of the stent DtempI,

[0100] 5.将支架冷却至低于TtransI。 [0100] 5. Place the rack to cool to below TtransI.

[0101] 当将两次编程的支架加热至高于TtransI时,DtraipI形状变为Dt„p2,即直径增大。当再次加热至高于Ttras2时,直径即为Dp_,即直径再次减小(图3)。 [0101] When the two programmed heating to stand above TtransI, DtraipI shape becomes Dt "p2, that is, the diameter increases. When was again heated to higher than Ttras2, diameter is Dp_, that is again reduced diameter (Fig. 3 ).

[0102] 现对本发明作进一步叙述。 [0102] The invention will now be described further.

[0103] 本发明的支架包括一种SMP材料。 [0103] The present invention includes a stent SMP material. 热塑性塑料、混合物和网络(network)都是适用的。 Thermoplastics, and mixtures thereof network (network) is applicable. SMP与无机纳米颗粒形成的复合材料也是适合的。 SMP composites formed with inorganic nanoparticles are also suitable. 优选不将加热元件包埋至SMP材料中。 The heating element is preferably not embedded to the SMP material. 形状记忆效应可以通过如下方式进行热激活:可加热介质、进行IR或NIR照射、施加振荡电场或进行UV照射。 Shape memory effect can be thermally activated by the following manner: a heating medium can be carried IR or NIR irradiation, the oscillating electric field is applied or UV irradiation.

[0104] 关于“本发明的支架包括一种SMP材料”的定义应当解释为,一方面支架基本由SMP材料组成,而另一方面也可以是包埋或涂布有SMP材料的常规支架。 [0104] The definition of "the stent of the present invention comprises a SMP material" should be interpreted as, on the one hand by the SMP stent basic material, but it can also be embedded or coated with a conventional SMP scaffold material. 这两种主要的构造(construction)具有以下优点。 The two major structural (construction) has the following advantages.

[0105] 主要由SMP材料组成的支架采用SMP材料确定支架的机械性能。 [0105] material composed mainly of SMP stent using SMP material to determine the mechanical properties of the stent. 由于SMP材料(将马上进行描述)是出于上述目的而使用的,从而确保了良好的组织相容性。 Since the SMP material (which will be described soon) is used for the purposes stated above, in order to ensure a good histocompatibility. 而且,如上所述,这种支架可以通过微创外科手术植入并移除。 Further, as described above, this stent can be implanted and minimally invasive surgical removal. SMP材料的加工亦相对容易,有助于促进生广。 SMP processed material is also relatively easy to help promote Guangsheng. 最后,SMP材料可以与其它物质复合或者层合,从而有可能进一步官能化。 Finally, SMP material may be a composite with other materials, or laminated, which may be further functionalized. 有关上述方面可参考以下叙述。 Refer to the following aspects related to the above described.

[0106] 原则上可行的第二个实施方案是一种包括有常规基本框架的支架,所述基本框架有例如“金属丝网状结构”或可变形管。 [0106] In principle, a second possible embodiment comprising a bracket with a conventional basic framework, for example, the basic framework "wire mesh structure" or deformable tube. 这种基本框架涂布有SMP材料或包埋于其中。 This basic framework is coated with SMP material or embedded therein. 特别地,金属丝网状构造已经证实,如果激活形状记忆效应,则SMP材料可以产生足够大的力,从而使基本框架发生变形。 In particular, a wire mesh-like structure has been confirmed, if activated shape memory effect, the SMP material can generate sufficient force, so that deformation of the basic framework. 因此,这一实施方案可以将常规支架的优势性能与SMP材料的上述有益效应结合起来。 Thus, this embodiment can be performance advantages of conventional stents with the above beneficial effects SMP material together. 从而特别地,借助于常规基本框架可以获得机械阻力很大的支架。 Whereby particular, can be obtained by means of conventional basic framework scaffold great mechanical resistance. 因此这一实施方案特别适用于机械载荷高的支架。 Therefore, this embodiment is particularly suitable for high mechanical load bracket.

[0107] 通过适当涂层(例如水凝胶涂层)或者表面微结构处理,支架表面与使用位置处的生理环境相容。 [0107] By suitable coating (eg hydrogel coating) or surface microstructure processing, physiological environment stent surface compatible with the use of a position. 在支架设计上,必须依据使用位置考虑基本条件,例如pH值或微生物数量。 The stent design, basic conditions must be considered based on the use of location, such as pH value or number of microorganisms.

[0108] 现对适合于本发明支架的材料进行叙述。 [0108] is now suitable for the present invention of the stent material will be described.

[0109] 本发明意义中的SMP材料是一种由于其化学-物理结构而能够发生所需形变的材料。 [0109] sense of the present invention, the SMP material is a due to its chemical - physical structure and material required deformation can occur. 除了实际的永久形状之外,这种材料还具有另一种可临时外加于其上的形状。 In addition to the actual permanent shape, this material also has the shape of another temporarily applied thereon. 这种材料的特征在于如下两个结构特点:网络结点(network point)(物理或共价)以及转换段。 This material is characterized by the following two structural features: network nodes (network point) (physical or covalent) and switching segments.

[0110] 具有热诱导形状记忆效应的SMP具有至少一个转换段,其形变温度即为转换温度。 [0110] thermally induced shape-memory effect of SMP has at least one transition section, its deformation temperature is the transition temperature. 转换段形成暂时的交联部分,该部分在加热至高于形变温度时发生解析,而冷却时又会再次形成。 Switching segments form temporary crosslinking part, parsing occurs when the part is heated to a temperature above the deformation temperature, while cooling will form again. 形变温度可以是无定形状态时的玻璃化温度Tg或者结晶状态时的熔融温度Tm。 The glass transition temperature can be deformation temperature Tg of the amorphous state or the crystalline melting temperature Tm state. 这里通常表示为Ttrans。 Here it is usually expressed as Ttrans. 在这一温度下,SMP发生形状上的改变。 At this temperature, SMP change shapes.

[0111] 高于Ttans时,材料处于无定形状态并具有弹性。 [0111] Above Ttans, the material is in an amorphous state and has elasticity. 如果将样品加热至高于形变温度Ttans,并使其在柔软的状态下发生变形,然后冷却至低于形变温度,则根据凝固自由度,链段将固定为变形状态(编程)。 If the sample is heated to above the deformation temperature Ttans, and allowed to deform in a soft state, and then cooled to below deformation temperature, according to the degree of freedom of solidification, the fixed segment deformed state (programmed). 形成的暂时交联部分(非共价)使样品在没有外加载荷的情况下也不能恢复其原始形状。 Temporarily crosslinked part (non-covalent) to form the sample in the absence of applied load does not return to its original shape. 当再次加热至高于形变温度时,这些暂时的交联部分解析,样品恢复为其原始形状。 When heated again to above the deformation temperature, these temporary crosslinking part analysis, the sample returns to its original shape. 通过再编程,可以再次产生临时的形状。 By re-programming, it can produce a temporary shape again. 再次得到的原始形状的精度表示为回复率(resetting ratio)。 The accuracy of the original shape once again expressed as response rate (resetting ratio).

[0112] 在光转换的SMP中,光反应活性基团取代了转换段的作用,所述光反应活性基团可通过光照射相互可逆连接。 [0112] SMP in optical conversion in the light reactive group replaced the role of the conversion period, the light reactive groups may be reversibly interconnected by light irradiation. 这时,通过照射实现临时形状的编程以及永久形状的再次形成,而不一定改变温度。 At this time, by irradiating achieve temporary shape and a permanent shape programming formed again, without necessarily changing the temperature.

[0113] 所有用于制造支架的SMP材料基本上均可使用。 [0113] All materials used to manufacture stents SMP basically can be used. 作为实例,可参考以下申请中所述的材料及制造方法,以下申请通过援引的方式直接归于本申请的内容中: As an example, refer to the following application materials and manufacturing methods described in the following apply directly attributable to this application by reference in its contents:

[0114]德国专利申请:10208211. 1,10215858. 4,10217351. 4,102173050. 8,10228120. 3、10253391.1,10300271. 5,10316573. 8。 [0114] German patent application:....... 10,208,211 1,10215858 4,10217351 4,102173050 8,10228120 5,10316573 3,10253391.1,10300271 8.

[0115]欧洲专利申请:99934294. 2、99908402. 3。 [0115] European Patent Application: 99934294 2,99908402 3.

[0116] 具有两种记忆形状的SMP材料在美国专利US 6,388,043中有述,所述专利通过援引的方式包括在本申请中。 [0116] SMP has two shape memory material is described in US patent US 6,388,043, the patent by invoking methods such as in the present application.

[0117] 以下为可在本发明的框架内、特别是在上述第二个实施方案中使用的常规支架材料: [0117] The following conventional scaffold to be within the framework of the invention, especially used in the above second embodiment:

[0118] 基本上适用于医药领域的生物稳定的材料有聚乙烯(PE)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、PVC、聚碳酸酯(PC)、聚酰胺(PA)、聚四氟乙烯(PTFE)、聚甲基丙烯酸酯、聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸羟乙酯(PHEMA)、聚丙烯酸酯、聚亚胺酯(TOR)、聚硅氧烷、聚醚醚酮(PEEK)、聚砜(PSU)、聚醚、聚烯烃、聚苯乙烯。 [01] basically applied to medicine in the field of bio-stable materials are polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), PVC, polycarbonate (PC), poly amide (PA), polytetrafluoroethylene (PTFE), polymethyl acrylate, polymethyl methacrylate (PMMA), poly-hydroxyethyl methacrylate (PHEMA), polyacrylate, polyurethane (TOR ), polysiloxanes, polyether ether ketone (PEEK), polysulfone (PSU), polyether, polyolefin, polystyrene.

[0119] 已经确定可用于无血管区的材料有,例如聚硅氧烷(导管及管状探针、人造膀胱)、PHEMA (人造膀胱)以及PA (导管)。 [0119] have been used to determine the avascular zone material, such as silicone (catheters and tubular probes, artificial bladder), PHEMA (artificial bladder) and PA (catheter).

[0120] 已经确定可用于血管区的材料有,例如TOR(人造血管、心瓣膜)、PET(人造血管、血管包覆物(coating))、PA( 二尖瓣)、聚硅氧烷(心瓣膜)、PTFE(管植入物)。 [0120] blood vessels has been determined that the material region can be used are, for example TOR (artificial blood vessels, heart valves), PET (artificial blood vessel, vascular wrap (coating)), PA (mitral valve), silicone (Heart valve), PTFE (implant).

[0121]为制造本发明的支架,可使用热塑性高弹体。 [0121] for the manufacture of the stent of the present invention may be a thermoplastic elastomer. 适合的热塑性高弹体的特征在于具有至少两个形变温度。 Characteristics of suitable thermoplastic elastomer is characterized by having at least two deformation temperature. 较高的形变温度可以规定为决定支架永久形状的物理网络结点。 Higher deformation temperature can be defined as the permanent shape of the stent determine the physical network nodes. 而可以激活形状记忆效应的较低的形变温度则可与转换段相关(转换温度,Ttans)。 The shape memory effect can be activated lower deformation temperature can be associated with the transition section (transition temperature, Ttans). 就适合的热塑性高弹体而言,转换温度一般高于体温约3至20C。 On suitable thermoplastic elastomers, the transition temperature is generally higher than the temperature of about 3 to 20 C.

[0122] 热塑性高弹体的实例有多嵌段共聚物。 [0122] Thermoplastic elastomers multiple instances of a block copolymer. 优选地,组成多嵌段共聚物的嵌段(大分子二醇(macrodiole))由下列α、ω 二醇聚合物组成,或者由所述二醇聚合物单体的α、ω二醇共聚物组成,所述α、ω 二醇聚合物包括••聚(ε -己内酯)(PCL)、聚乙二醇(PEG)、聚十五内酯、聚环氧乙烷、聚环氧丙烷、聚丙二醇、聚四氢呋喃、聚对二氧环己酮、聚丙交酯、聚乙交酯、聚(丙交酯-乙交酯)(poly (lactide-ranglycolid))、聚碳酸酯以及聚醚,所述多嵌段共聚物的分子量1为250至500,000g/mol。 Preferably, the diol from the polymer monomer α, ω diol block copolymers multiblock copolymer (macromer diol (macrodiole)) represented by the following α, ω-diol polymer, or composition, the α, ω-diol •• polymers include poly (ε - caprolactone) (PCL), polyethylene glycol (PEG), poly fifteen lactones, polyethylene oxide, polypropylene oxide , polypropylene glycol, polytetrahydrofuran, poly dioxanone, polylactide, polyglycolide, poly (lactide - glycolide) (poly (lactide-ranglycolid)), polycarbonate, and polyether, The multi-block copolymer of molecular weight 1 250 to 500,000g / mol. 借助于适合的双官能偶合试剂(特别是脂肪族二异氰酸酯或芳族二异氰酸酯或二酸式氯化物(di-acid chloride)或光气),将两种不同的大分子二醇相连,从而形成分子量500至50,000,000g/mol的热塑性高弹体。 By means of suitable bifunctional coupling agent (particularly an aliphatic diisocyanate or an aromatic diisocyanate or the acid chloride of formula (di-acid chloride) or phosgene), to connect two different macroglycol to form a molecular weight of 500 to 50,000,000g / mol thermoplastic elastomer. 在相分离聚合物(phase-segregated polymer)中,上述聚合物各嵌段中的一个相伴随有至少一种热转变(玻璃化转变或熔融转变),而与另外的嵌段无关。 In the phase separation of the polymer (phase-segregated polymer), the above polymer in each block is accompanied by a phase of at least one thermal transition (glass transition or melting transition), irrespective of the other block.

[0123] 特别优选基于十五内酯(TOL)和-己内酯(PCL)的大分子二醇与二异氰酸酯形成的多嵌段共聚物。 [0123] Particularly preferred based pentadecanolide (TOL) and - caprolactone (PCL) macroglycol with a diisocyanate forming a multi-block copolymer. 转变温度——此时为熔融温度——可以通过改变PCL的嵌段长度设定在约30至55C的范围内。 Transition temperature - in this case, the melting temperature of - PCL by changing the block lengths in the range of about 30 to 55 C for. 固定支架永久形状的物理网络结点通过熔点87至95C的第二结晶相形成。 Physical network node fixation permanent shape by the second crystallization temperature 87 至 95 C of phase formation. 多嵌段共聚物的混合物也是适合的。 Mixtures of block copolymers are also suitable. 形变温度可以通过混合比以目标方式设定。 Deformation temperature can be set in a targeted manner by mixing ratio.

[0124] 为制造本发明的支架,也可以使用聚合物网络。 [0124] for the manufacture of the stent of the present invention may also be used a polymer network. 适合的聚合物网络的特征在于共价网络结点以及具有至少一个形变温度的至少一种转换元件。 Suitable characterized in that the covalent polymer network and a network node having at least one deformation temperature of at least one conversion element. 共价网络结点决定了支架的永久形状。 Covalent network node determines the permanent shape of the stent. 就适合的聚合物网络而言,转换温度通常高于体温约3至20C,在该温度下形状记忆效应可以被激活。 For the purposes of the polymer network, the transition temperature is usually higher than the temperature of about 3 to 20 C, at which temperature the shape memory effect can be activated.

[0125] 为形成共价聚合物网络,上述一种大分子二醇通过多官能偶合试剂交联。 [0125] To form the covalent polymer network, said polyfunctional glycols macromolecules cross-linked by coupling agent. 这种偶合试剂可以是至少三官能的低分子量化合物或者多官能聚合物。 Such coupling agent may be at least trifunctional low molecular weight compound or a polyfunctional polymer. 就聚合物而言,可以是至少三个臂的星形聚合物、至少两个侧链的接枝聚合物、超支化聚合物或者树枝状结构。 To polymers, star polymers may be at least three arms, at least two side chains of the graft polymer, a dendritic or hyperbranched polymer structure. 就低分子量化合物及聚合化合物而言,端基必须能够与二醇反应。 For the purposes of low molecular weight compounds and polymeric compounds, the end groups must be able to react with the diol. 为达到此目的,可特别使用异氰酸酯基团(聚亚胺酯网络)。 To achieve this purpose, especially isocyanate groups (polyurethane networks).

[0126] 特别优选三醇和/或四醇与二异氰酸酯形成的无定形聚亚胺酯网络。 [0126] Particularly preferred triols and / or tetrols amorphous polyurethane networks and diisocyanate formation. 在单体熔融且有羟基官能引发剂存在的情况下,通过加入氧化二丁基锡(IV) (DBTO)催化剂,使外消旋二丙交酯与二乙交酯发生开环共聚得到代表性的星形预聚物,例如低聚[(外消旋乳酸)_共聚-甘醇酸酯]三醇或四醇。 In the melting and hydroxy-functional monomer when the presence of the initiator, by adding dibutyltin oxide (IV) (DBTO) catalyst, dipropyl racemic lactide and diethyl lactide ring-opening copolymerization representative stars shaped prepolymers, such as oligo [(rac-lactic acid) copolymer _ - glycolate] triol or tetraol. 开环聚合反应的引发剂使用乙二醇、1,1,I-三(羟甲基)乙烷或季戊四醇。 Ring-opening polymerization initiator ethylene glycol, 1,1, I- tris (hydroxymethyl) ethane or pentaerythritol. 类似地,制备出低聚(乳酸-共聚-羟基己酸酯)四醇及低聚(乳酸-羟基乙氧基乙酸酯)以及[低聚(丙二醇)_嵌段-低聚(外消旋乳酸)_共聚-甘醇酸酯]]三醇。 Similarly prepared oligo (lactic acid - copolymer - hydroxy hexanoate) tetraol and oligo (lactic acid - hydroxyethoxy acetate), and [oligo (propylene glycol) block _ - oligo (rac lactic acid) copolymer _ - glycolate]] glycerol. 本发明网络可易于通过如下方法获得:在诸如二氯甲烷的溶剂中用二异氰酸酯,例如2,2,4-与2,4,4-三甲基己烷-I,6- 二异氰酸酯(TMDI)的同分异构混合物转化预聚物,并随后干燥。 Network of the present invention can be easily obtained by the following method: in dichloromethane solvent with a diisocyanate such as, for example, 2,2,4 and 2,4,4-trimethyl hexane -I, 6- diisocyanate (TMDI ) isomeric mixture into the prepolymer, and then dried.

[0127] 而且,上述大分子二醇还可以官能化为相应的可进行热交联或者光化学交联的α、ω-二乙烯基化合物。 [0127] Further, the above-described molecules may be functionalized to the corresponding diols can be crosslinked thermally or photochemically crosslinked α, ω- divinyl compounds. 优选地,官能化能够通过不产生副产物的反应实现大分子单体的共价连接。 Preferably, the functionalized through the reaction does not produce byproducts achieve macromers covalently connected. 这种官能化优选由烯键式不饱和单元提供,特别优选由丙烯酸酯基团以及甲基丙烯酸酯基团提供,其中特别优选后者。 Such functionalization is preferably provided from ethylenically unsaturated units, particularly preferably provided by acrylate groups and methacrylate groups, the latter being especially preferred. 这时,特别地,可以在适合碱的存在下,通过与相应的酰基氯反应,转化为α、ω-大分子二甲基丙烯酸酯或大分子二丙烯酸酯。 In this case, in particular, it can be in the presence of a suitable base, by reaction with the corresponding acid chloride into α, ω- or dimethacrylate macromer diacrylate macromer. 端基官能化的大分子单体发生交联,从而获得网络。 End-functional crosslinking macromonomers to obtain network. 这种交联可以通过照射熔融物实现,所述熔融物包括有端基官能化的大分子单体,还可能包括有低分子量共聚单体,有关内容将在下文中进一步予以解释。 Such crosslinking can be realized by irradiating the melt, the melt comprises end groups functionalized macromer may also include a low molecular weight comonomer, materials for further be explained hereinafter. 其适合的方法条件为,优选40至100C温度下、优选308nm波长的光照射熔融混合物。 Suitable method conditions for which, at preferably 40 to 100 C temperature, the molten mixture is preferably irradiated with 308nm wavelength light. 或者,如果使用相应的引发剂体系,也可以进行热交联。 Or, if you are using the appropriate initiator systems can also be thermally crosslinked.

[0128] 上述大分子单体发生交联时,如果使用一种类型的大分子单体,则形成结构均匀的网络。 [0128] said macromer crosslinking, if one type of macromonomer, the formation of a homogeneous network structure. 如果使用两种类型的单体,则获得AB型网络。 If two types of monomer, is obtained AB-type network. 如果官能化大分子单体与适合的低分子量化合物或低聚化合物共聚,则可以获得这种AB型网络。 If functional macromer with a suitable low molecular weight compounds or oligomeric compounds copolymerized AB can be obtained such networks. 用丙烯酸酯基团或甲基丙烯酸酯基团官能化大分子单体时,适合的可共聚的化合物为低分子量丙烯酸酯、甲基丙烯酸酯、二丙烯酸酯或二甲基丙烯酸酯。 When using acrylate groups or methacrylate groups functionalized macromer, suitable compounds copolymerizable low molecular weight acrylate, methacrylate, diacrylate or dimethacrylate. 这类化合物优选丙烯酸酯(例如丙烯酸丁酯或丙烯酸己酯)及甲基丙烯酸酯(例如甲基丙烯酸甲酯及甲基丙烯酸羟乙酯)。 Such compounds are preferably acrylates (e.g. butyl acrylate or hexyl acrylate), and methacrylic acid esters (e.g., methyl methacrylate and hydroxyethyl methacrylate).

[0129] 这种可与大分子单体共聚的化合物的量可以是大分子单体与低分子量化合物网络的5至70重量%,优选15至60重量%。 [0129] The amount of the compound that can be copolymerized with the macromonomer may be from 5 to 70% by weight of macromonomer network and low molecular weight compounds, preferably 15 to 60 wt%. 通过将相应量的化合物加入至待交联的混合物中进行低分子量化合物的变量接入(installation)。 Low molecular weight compounds by the corresponding amount of the compound is added to the mixture to be crosslinked were variable access (installation). 接入网络中的低分子量化合物的量与交联混合物的量对应。 The amount of the access network corresponding to low molecular weight compounds and the amount of the crosslinking mixture.

[0130] 现对本发明使用的大分子单体进行详细阐述。 [0130] The present invention is now to be used macromonomer be elaborated.

[0131] 通过改变大分子二醇的摩尔量,可以获得具有不同交联密度(或片段长度)及机械性能的网络。 [0131] By changing the molar amount of the macromolecular diol can be obtained with different crosslink density (or fragment length) and mechanical properties of the network. 通过GPC分析确定的共价交联大分子单体的数均摩尔量优选为2000至30000g/mol,优选500至20000g/mol,特别优选7500至15000g/mol。 Determined by GPC analysis, the number of covalent cross-GA-average molar amount of the monomer molecule is preferably from 2000 to 30000g / mol, preferably 500 to 20000g / mol, particularly preferably from 7500 to 15000g / mol. 共价交联的大分子单体优选在其链的两端均存在甲基丙烯酸酯基团。 Covalent crosslinking macromers are present preferably methyl acrylate groups at both ends of its chain. 这种官能化使大分子单体能够通过简单的光引发(照射)即发生交联。 This functional macromonomer can make a simple photo-initiator (exposure) that is crosslinked.

[0132] 大分子单体优选为生物稳定的或者降解非常慢的聚酯大分子单体,特别优选基于-己内酯或十五内酯的聚酯大分子单体。 [0132] macromer preferably biostable or degradable polyester macromer very slow, particularly preferably based on - caprolactone or fifteen lactone polyester macromer. 其它可能的聚酯大分子单体基于丙交酯单元、乙交酯单元、对二氧环己酮单元及其混合物,以及带有-己内酯单元的混合物,其中特别优选带有己内酯单元或十五内酯单元的聚酯大分子单元。 Other possible based polyester macromer lactide units, glycolide units of dioxanone units and mixtures thereof, and with - a mixture of caprolactone units, particularly preferred with caprolactone unit or pentadecanolide unit of polyester macromolecules unit. 优选的聚酯大分子单体还有聚(己内酯-共聚-乙交酯)以及聚(己内酯-共聚-丙交酯)。 The preferred polyester macromer also poly (caprolactone - copolymer - glycolide) and poly (caprolactone - copolymer - lactide). 形变温度可以通过共聚单体的用量比来设定。 Deformation temperature can be set by using the ratio of comonomer. 特别优选的还有基于聚醚、聚碳酸酯、聚酰胺、聚苯乙烯、聚对苯二甲酸丁二醇酯以及聚对苯二甲酸乙二醇酯的生物稳定的大分子单体。 Also particularly preferred are polyether-based, polycarbonate, polyamide, polystyrene, polyethylene terephthalate, polybutylene terephthalate and polyethylene biological terephthalate stabilized macromonomer.

[0133] 本发明特别优选使用的大分子单体是包括有可连接端基的聚酯、聚醚或聚碳酸酯。 [0133] Particularly preferred macromonomer of the present invention is used comprising a connectable polyester, polyether or polycarbonate end groups. 本发明使用的特别优选的聚酯为基于-己内酯或十五内酯的聚酯,其摩尔量如上文所述。 Particularly preferred polyesters of the present invention is based on the use of - caprolactone or fifteen lactone polyester, the molar amount thereof as described above. 这种两端被官能化、优选用甲基丙烯酸酯基团官能化的聚酯大分子单体产品,可以通过本领域技术人员已知的简单合成方法来制造。 Such ends are functionalized, preferably with methacrylate groups functionalized polyester macromer product may be known to those skilled in the simple synthetic methods to produce. 在不考虑本发明的其它主要聚合物组分的情况下,这种网络表现出半结晶性能,并且其熔点为聚酯组分的熔点(可由DSC测量方法确定),即该熔点取决于所用聚酯组分的种类,并且可以由其控制。 Without considering other primary polymer components of the present invention, the network that exhibits a semi-crystalline properties, and a melting point of the melting point of the polyester component (determined by the DSC measuring method), i.e. depending on the melting point of the poly ester component types, and can be controlled by it. 已知对于基于己内酯单元的片段而言,这一温度(TmI)在30至60C之间,取决于大分子单体的摩尔量。 For fragments based on known terms caprolactone unit, the temperature (TmI) between 30 and 60 C, depending on the molar amount of the macromonomer.

[0134] 以熔融温度作为转变温度的优选网络基于大分子单体聚(己内酯-共聚-乙交酯)二甲基丙烯酸酯。 [0134] In the melting temperature transition temperature as network-based macromer is preferably poly (caprolactone - copolymer - glycolide) dimethacrylate. 大分子单体可以转化为这种形式,或者与丙烯酸正丁酯共聚形成AB网络。 Macromonomer can be converted to this form, or the formation of n-butyl acrylate copolymer AB network. 支架的永久形状由共价网络结点决定。 Permanent shape bracket is determined by the covalent network nodes. 这种网络的特征在于结晶相的熔点可以通过,例如己内酯与乙交酯的共聚单体比例以目标方式设定在20至57C范围内。 Characteristics of such a network is that the melting point of the crystalline phase can be obtained, for example caprolactone and glycolide copolymerized monomer ratio is set in a targeted manner in the range of 20 to 57 C range. 可以将例如,丙烯酸正丁酯用作共聚单体,使支架的机械性能最优化。 May be, for example, n-butyl acrylate as a comonomer, the mechanical properties of the stent optimization.

[0135] 以玻璃化温度作为转变温度的另一个优选网络是以ABA三嵌段二甲基丙烯酸酯作为大分子单体获得的,这种网络的特征在于中心嵌段B为聚环氧丙烷,而末端嵌段A为聚(外消旋丙交酯)。 [0135] In a glass transition temperature as the temperature is further preferred network ABA triblock dimethacrylate as macromonomer obtained, characterized in that the center of this network is polypropylene oxide block B, The terminal block A is poly (rac-lactide). 无定形网络的转换温度的范围非常宽。 Amorphous network transition temperature range is very wide.

[0136] 为制备具有两种记忆形状的支架,具有两个形变温度的网络是适合的,例如互穿网络(IPN)。 [0136] To prepare the stent has two memory shape, having two deformation temperature of the web is appropriate, such as interpenetrating networks (IPN). 共价网络基于作为大分子单体的聚(己内酯)_ 二甲基丙烯酸酯;互穿组分为基于十五内酯(TOL)及-己内酯(PCL)的大分子二醇与二异氰酸酯的多嵌段共聚物。 Covalent network-based macromer as poly (caprolactone) dimethacrylate _; interpenetrating component based on fifteen lactone (TOL), and - caprolactone (PCL) with the macromolecule diol multi-block copolymer of a diisocyanate. 材料的永久形状由共价网络结点决定。 Permanent shape of the material is determined by the covalent network nodes. 两个形变温度——结晶相的熔融温度——可以作为临时形状的转换温度。 Two deformation temperature - crystalline phase melting temperature - can be used as a temporary form of the transition temperature. 较低的转换温度Ttrans可通过PCL的嵌段长度设定在约30至5C之间。 Ttrans lower transition temperature can be set between about 30 and 5 C by PCL block length. 较高的转换温度Ttrans2在87至95C之间。 Higher conversion temperatures between 87 Ttrans2 至 95 C.

[0137] 上述SMP材料主要基于聚酯或低聚酯片段。 [0137] Based on the above SMP materials mainly polyester or oligoester fragment. 因此,尽管对于大多数应用而言稳定性是足够的,然而,由于酯键相对容易发生水解分解,故而这种SMP材料在生理环境中有个别表现出稳定性不够,特别是对于未在使用位置处保留很长时间的支架。 Thus, although for most applications is sufficient stability, however, since the ester bond is relatively prone to hydrolytic degradation, and therefore such material individual SMP exhibit a physiological environment stability is not enough, especially for the position is not in use It reserves the stand for a long time. 然而,此类问题可以通过使SMP材料包括基于聚醚或低聚醚单元或者聚碳酸酯或低聚碳酸酯单元的片段加以克服。 However, such problems can be overcome to make SMP material comprises a polyether-based segment or low polyether units or polycarbonate or oligocarbonate unit.

[0138] 此类片段可基于,例如聚环氧乙烷、聚环氧丙烷或者聚环氧丁烷。 [0138] Such fragments may be based, e.g., polyethylene oxide, polypropylene oxide or polybutylene oxide.

[0139] 为制备本发明的支架,还可以使用光敏性网络。 [0139] The stent preparation of the present invention may also be used photosensitivity network. 适合的光敏性网络是无定形的,并且其特征在于决定支架永久形状的共价网络结点。 Suitable photosensitive networks are amorphous, and is characterized in that the network node decides covalently permanent shape of the stent. 另一个特征是可以利用光发生可逆转换的光反应活性组分或单元,该组分或者单元决定支架的临时形状。 Another feature is the use of temporary shape of the light-reactive component or unit reversible conversion of light occurs, the component or unit decides bracket.

[0140] 就感光聚合物而言,所使用的适合的网络在无定形链段上带有光敏性取代基。 [0140] For the photosensitive polymers suitable for use with network photosensitive substituents in the amorphous segments. 当有UV光照射时,这些基团能够相互形成共价键。 When a UV light irradiation, these groups capable of forming a covalent bond to each other. 如果材料发生变形,并被适当波长λΐ的光照射,则原网络也会发生交联。 If the material is deformed and irradiated with light of the appropriate wavelength λΐ, the original network will crosslink. 由于交联的发生,材料将在变形状态下暂时固定(编程)。 Crosslinking occurs, the material will be deformed state temporarily fixed (programmed). 由于光连接可逆,因此可以用不同波长λ 2的光再进行照射,从而再次解除交联,这样就可以再现出材料的原始形状(再现)。 Since the optical connection reversible, so you can use different wavelength λ 2 is then irradiated with light, thereby again releasing crosslinking, so that you can reproduce the original shape of the material (reproduction). 这种光-机械循环通常可以随意地反复。 This light - mechanical cycle can usually be freely again. 光敏性材料的基础是大网眼聚合物网络,如上所述,这种网络对于旨在激活形变的照射而言是透明的,也就是说优选形成UV透明基体。 Based photosensitive polymer materials are large mesh networks, as described above, such a network is transparent to the intended activation of irradiation in terms of deformation, i.e. preferably UV transparent substrate is formed. 依据本发明,优选的本发明网络以低分子量的丙烯酸酯及甲基丙烯酸酯为基础,并且可以激发聚合,特别是甲基丙烯酸的C1-C6酯以及羟基衍生物,其中优选丙烯酸羟乙酯、甲基丙烯酸羟丙酯、聚甲基丙烯酸乙二醇酯及丙烯酸正丁酯;优选使用丙烯酸正丁酯以及甲基丙烯酸羟乙酯。 According to the present invention, the network of the present invention is preferably a low molecular weight acrylate and methacrylate based, and can stimulate the polymerization, especially methacrylic acid esters of C1-C6, and hydroxyl derivative, which preferably hydroxyethyl acrylate, hydroxypropyl methacrylate, polyethylene glycol methacrylate and acrylate, n-butyl; n-butyl acrylate is preferably used, and hydroxyethyl methacrylate.

[0141] 一种组分被用作制备本发明聚合物网络的共聚单体,该组分的作用在于使片段发生交联。 [0141] A polymer network components are used in the preparation of the present invention comonomer effect of this component is to make the segment crosslinking. 这一组分的化学性质当然取决于单体的性质。 Chemical nature of the components, of course, depend on the nature of the monomers.

[0142] 对于上述基于丙烯酸酯单体的优选网络而言,适合的交联剂为双官能丙烯酸酯化合物,这种化合物可与链段的原料适当反应,从而可以与其一同转化。 [0142] For the purposes of the above-described preferred network based on acrylate monomers, difunctional acrylate compound suitable crosslinking agent, such a compound may be reacted with the appropriate starting material segment, thereby transforming together therewith. 此类交联剂包括双官能短链交联剂(short cross linkingagent)(例如二丙烯酸乙烯酯)、低分子量双官能或多官能交联剂、低聚物、直链二丙烯酸酯交联剂(例如聚(氧乙烯)二丙烯酸酯或聚(氧丙烯)二丙烯酸酯)以及带有丙烯酸酯端基的支链低聚物或聚合物。 Such short chain difunctional crosslinkers include crosslinkers (short cross linkingagent) (e.g., two vinyl acrylate), a low molecular weight bifunctional or polyfunctional crosslinking agents, oligomers, linear diacrylate crosslinker ( e.g., poly (ethylene oxide) diacrylate or poly (oxypropylene) diacrylate), and branched oligomers or polymers with terminal acrylate groups.

[0143] 本发明的网络包括光反应活性组分(基团)作为另一种组分,其作用亦在于以目标方式控制形变的激活。 [0143] network of the present invention comprises a light-reactive components (groups) as another component, its effect also in that the controlled deformation of the target activation. 光反应活性基团是一个能够在适合的光照射刺激下,优选UV照射(带有第二光反应活性基团)下,进行可逆反应的单元,从而引起共价键的生成或者解析。 Light is a reactive group capable under appropriate stimulus light irradiation, preferably UV irradiation (with the second photoreactive group), reversible reaction unit, thereby causing the generation of a covalent bond or resolution. 优选的光反应活性基团是能够发生可逆光二聚反应的基团。 The preferred light reactive groups are capable of reversible light dimerization reaction occurs group. 作为本发明光敏性网络中的光反应活性组分,可以优选使用不同的肉桂酯(CA)以及丙烯酸肉桂酯(CAA)。 As in the present invention, an optical network photosensitive reactive components, preferably used may be different cinnamyl ester (CA), and cinnamyl acrylate ester (CAA).

[0144] 已知肉桂酸及其衍生物在约300nm的UV光下通过形成环丁烷发生二聚反应。 [0144] cinnamic acid and its derivatives known in about 300nm under UV light to form a cyclobutane by the dimerization reaction. 如果用约240nm的较短波长照射,则二聚物还可以再分离。 If you use a shorter wavelength of about 240nm illumination, the dimer may also be separated again. 苯环上的取代基可以改变最大吸收,但通常还是处于UV范围内。 Substituents on the benzene ring can change the maximum absorption, it is usually in the UV range. 其它可以光二聚的衍生物为I,3- 二苯基-2-丙烯-I-酮(查耳酮)、肉桂基丙烯酸、4-甲基香豆素、不同邻位取代的肉桂酸、肉桂酰氧基硅烷(肉桂醇的甲硅烷基醚)。 Other possible light dimeric derivatives I, 3- diphenyl-2-propene-one -I- (chalcone), cinnamyl acrylate, 4-methyl-coumarin, different ortho-substituted cinnamic acid, cinnamic acyloxy silane (cinnamyl alcohol silyl ether).

[0145] 肉桂酸与类似衍生物的光二聚反应为双键的[2+2]环加成,得到环丁烷衍生物。 [0145] cinnamic acid and derivatives light dimerization reaction similar to the double bond [2 + 2] cycloaddition to give cyclobutane derivative. E-异构体和Z-异构体均能够发生该反应。 Isomers E- and Z- isomers are the reaction to occur. 在光照射下,E/Z异构化与环加成竞争进行。 Upon irradiation with light, E / Z isomerization and cycloaddition competition conducted. 但结晶状态时E/Z异构化会被抑制。 But the crystalline state E / Z isomerization is suppressed. 由于异构体相互之间有不同的排列,理论上可以产生11 种不同的立体异构产物(古柯间二酸、古柯邻二酸)。 Because there are different arrangements between each other isomer, in theory, can produce 11 different stereoisomeric products (coca between acid, phthalic acid, coca). 该反应所需的两个肉桂酸基团之间双键的键长为约4 A。 Necessary for the reaction between two groups of cinnamic acid double bond length of about 4 A.

[0146] 网络的特征如下所述: [0146] characteristics of the network as follows:

[0147] 总体而言,网络为回复值较高的有益的SMP材料,也就是说在多次进行循环形变之后仍然以较高的百分比恢复原始形状,通常高于90%。 After [0147] In general, the higher the value of the network to respond useful SMP material, i.e. repeated cycles of deformation at still higher percentage recovery of the original shape, usually higher than 90%. 未发生不利的机械性能损失。 Disadvantageous loss of mechanical properties did not occur.

[0148] 为提高血液相容性,可以改造本发明使用的SMP材料的化学结构,例如通过接入上述聚醚或低聚醚单元。 [0148] To improve the blood compatibility, it can transform the chemical structure of SMP materials in the present invention, e.g., through an access unit of the polyether or polyether low.

[0149] 将聚合物加工为支架 [0149] The scaffold polymer processing

[0150] 为将热塑性高弹体加工为,例如中空管等形式(图I)的支架,可以使用本领域技术人员已知的所有常规的聚合物工艺方法,例如注塑法、挤出法、快速成形法等等。 [0150] The thermoplastic elastomer processing, for example in the form of a hollow tube (Figure I) of the bracket, you can use this skill in the art of all conventional polymer technology methods, such as injection molding, extrusion, Rapid prototyping method and so on. 除此之夕卜,还可以使用诸如激光切割的制造方法。 In addition the evening Bu, you can also use manufacturing methods such as laser cutting. 就热塑性高弹体而言,可以通过下述方法实现不同设计:纺为单丝及多丝后交织为网眼结构的圆柱形网络。 On the thermoplastic elastomer, there can be realized by a method different designs: spinning after monofilament and multifilament interwoven mesh structure is cylindrical network.

[0151] 在制造聚合物网络的过程中需要注意的是,大分子单体交联反应的发生形式对应于支架的永久形状(注塑法、然后固化)。 [0151] In the process of production of the polymer network should be noted that, in the form of cross-linking reaction occurs macromonomer permanent shape corresponding to the holder (injection molding, and curing). 特别地,本发明的网络材料需要针对进一步的加工采取特殊的铣切方法。 In particular, the network material of the present invention, the need for special milling method for further processing. 建议利用适合波长的激光对管状制品进行穿孔或切割。 We recommend the use of suitable wavelength laser perforation or cutting of tubular products. 借助这种技术——特别是将CAD与脉冲CO2激光或脉冲YAG激光相结合——可以在不使材料受到较高热负载(以及由此在表面上产生的不需要的副反应)的情况下,制造出最高达20μπι大小的形状。 With this technology - especially the CAD and pulsed CO2 laser or pulsed YAG laser combined - can be made without the material by high thermal load (and undesired side reactions on the surface thus produced), the create up 20μπι size shape. 或者,建议通过去毛刺(chip removing)加工获得成品支架。 Alternatively, the proposal was finished stand by deburring (chip removing) process.

[0152] 通过适当的方法将常规材料(见上)涂布或包埋至SMP材料,以实现第二个实施方案。 [0152] by a conventional method suitable material (see above) to the SMP coating or embedding material, in order to achieve the second embodiment.

[0153] 支架所需的机械性能取决于使用位置,并要求进行相应的设计。 [0153] mechanical properties of the stent required depending on the location and requested appropriate design. 如果植入的支架受到强烈的机械变形,则需要非常高的柔韧性以使支架在运动过程中不致崩塌。 If the implanted stent by strong mechanical deformation, it requires a very high flexibility to the stent in the course of the campaign will not collapse. 基本上讲“金属丝线圈设计”更为合适。 Basically "wire coil design" is more appropriate. 在器官位置较深的其它区域,支架的机械负载较小,这一机械负载不是由于变形产生的,而是因为外压较高。 In other areas of deep organ location, the stent is small mechanical loads, the mechanical load is not generated due to the deformation, but because of the higher external pressure. 出于这一原因,适合的支架必须具有能对周围组织施加高径向力的特征。 For this reason, a suitable bracket must have features capable of applying high radial forces to the surrounding tissue. 这种情况下“开槽管设计”似乎更为合适。 In this case, "slotted tube design" seems more appropriate. 带穿孔的管可以使液体从周围组织流入支架内(引流)。 With perforated tube allows liquid to flow into the stent within the (drainage) from the surrounding tissue.

[0154] 特别地,现有技术经常会在直径较小的血管内出现问题,因为已知支架对于这种血管的柔韧性及适应性均不足。 [0154] In particular, the prior art often cause problems in the smaller diameter of the blood vessels, known as vascular stents were inadequate for such flexibility and adaptability. 然而,本发明的支架在这种血管中也能够安全使用,因为SMP材料的弹性优良,即在低挠度下具有高弹性并且在扩张较大时具有高强度,因此能够在诸如动脉的脉冲式运动的情况下保护血管。 However, the stent of the present invention in which blood vessels can also be used safely, because the elastic material excellent in SMP, i.e., having a high elasticity at low deflection and expansion of large high strength, it is possible to pulsed motion, such as the artery protect the blood vessels under the circumstances.

[0155] 由于就用于无血管区的支架而言引流效应是首要的,因此,特别地,包埋有常规基本框架的设计或者基本由SMP材料组成的设计(穿孔管或网状体)对于这种支架都是非常有益,因为在上述设计中引流所必需的流体渗透非常简单,而同时又表现出足够的机械强度。 [0155] Due to a holder for avascular zone in terms of drainage is the primary effect, therefore, in particular, are embedded design or basic design of the SMP material conventional basic frame (perforated tube or mesh body) for This holder is very useful, because in the above-described design of drainage fluid penetration required is very simple, but at the same time exhibiting sufficient mechanical strength.

[0156] 支架官能化 [0156] scaffold functionalized

[0157] 为了更方便地置入支架,可以给支架涂布一层提高其滑动性的涂层 [0157] In order to make it easier to stents, stent coating can give to improve the sliding layer coating

[0158](例如硅氧烷或水凝胶)。 [0158] (e.g., silicone or hydrogel).

[0159] 其它改善血液相容性的可行作法包括,提供涂层(就此目的而言所必需的材料为本领域技术人员已知)、或者可以进行表面微结构处理。 [0159] Other improved blood compatibility feasible approach includes providing a coating (material necessary for this purpose to the skilled artisan), or may be surface treated microstructure. 适合的表面改性方法有,例如等离子体聚合以及接枝聚合。 Surface modification methods are suitable, for example, plasma polymerization, and graft polymerization.

[0160] 为了通过可视诊断方法更简单地将支架定位,可以通过适合的X射线造影剂(例如BaSO4)遮蔽形状记忆塑性材料。 [0160] In order to pass the visual diagnostic method more simply position the stand, you can fit the X-ray contrast agent (such as BaSO4) shield shape memory plastic material. 另一种可行的作法是将金属丝线(例如不锈钢)装入支架内。 Another possible approach is to metal wires (such as stainless steel) into the stent. 这种金属丝线的作用不在于稳定(而在于定位);其目的仅在于增强X射线造影。 The role of this metal thread is not stable (and in that location); its sole purpose is to enhance the X-ray angiography. 第三种可行的作法是利用金属屏蔽,这种金属除了具有较强的X射线造影之外,还具有抑制病毒、杀真菌或杀细菌性能(例如纳米银)。 The third possible approach is to use a metal shield, in addition to the metal with a strong X-ray contrast media, but also inhibit the virus, fungicidal or bactericidal properties (e.g., nano-silver). 这方面的另一种替代方法是将诸如三碘苯衍生物的X射线不透明发色团引入SMP材料本身。 An alternative method such as this is the three-iodobenzene derivative chromophore X-ray opaque material itself is introduced SMP.

[0161] 在另一个实施方案中,SMP可以与无机纳米颗粒复合。 [0161] In another embodiment, SMP with inorganic nanoparticle composite. 实例为由镁或镁合金或者磁铁制成的颗粒。 Examples of particles by magnesium or magnesium alloy, or made of a magnet. 由碳制成的颗粒也是适合的。 Particles made of carbon are also suitable. 以这种方式官能化的SMP可以在振荡电场中加热以激活形状记忆效应。 In this way functionalized SMP can be heated in an oscillating electric field to activate the shape memory effect.

[0162] 本发明的支架中也可加入多种有疗效的物质,这些物质可以有助于治疗、可以抑制支架的再狭窄、或者还可预防后续疾病的发生。 [0162] stent of the present invention may also be added to a variety of curative substances that can contribute to the treatment can be suppressed again stent stenosis, or also to prevent the occurrence of subsequent disease. 可以特别采用以下物质: May in particular the following materials:

[0163]-抗炎活性物质(例如依沙吖啶) [0163] - Anti-inflammatory active substances (such as Ethacridine)

[0164]-止痛物质(例如阿司匹林) [0164] - analgesic substances (e.g., aspirin)

[0165]-抗生活性物质(例如依诺沙星、呋喃妥因) [0165] - Anti-living substances (such as enoxacin, nitrofurantoin)

[0166]-抗病毒、抗真菌活性物质(例如元素银) [0166] - antiviral, antifungal substances (such as elemental silver)

[0167]-抗凝血活性物质(例如AAS、氯吡格雷、水蛭素、来匹卢定、地西卢定) [0167] - anticoagulant active substances (such as AAS, clopidogrel, hirudin, lepirudin, Desirudin)

[0168]-抑制细胞活性物质(例如西罗莫司、瑞帕霉素或西罗莫司) [0168] - inhibition of cell active substances (such as sirolimus, rapamycin or sirolimus)

[0169]-免疫抑制活性物质(例如ABT-578) [0169] - immunosuppressive active material (e.g., ABT-578)

[0170]-降低再狭窄的活性物质(例如紫杉酚、紫杉醇、西罗莫司、放线菌素D)。 [0170] - reduce restenosis active substances (such as taxol, paclitaxel, sirolimus, actinomycin D).

[0171] 本发明的支架中可以以不同的方式加入活性物质。 [0171] stent of the present invention may be added to the active substance in different ways.

[0172] 所述活性物质可以用塑料直接遮蔽,或者将其作为涂层粘着至支架上。 [0172] The active substance can be directly used plastic shield, or its adhesion to the stent as a coating.

[0173] 此类支架也可用于基因治疗领域。 [0173] Such stents can also be used in gene therapy field.

[0174] 如果用活性物质直接遮蔽支架材料,则活性物质既可以以降解控制的方式释放,也可以以扩散控制的方式释放。 [0174] If the active substance directly masking scaffold, the active substance can be either released to degrade in a controlled manner, it can be diffusion controlled release manner. 降解控制释放时,活性物质从基体中扩散出来的速度慢于聚合物的降解速度。 When the degradation controlled release of active substance from the matrix diffusion out slower than the rate of degradation of the polymer. 这时,有利地,活性物质可包埋在包裹支架的可降解涂层中,或者直接包埋至聚合物内。 In this case, advantageously, the active substance can be entrapped in the biodegradable stent coating wrapped, or embedded directly into the polymer. 扩散控制释放时,活性物质从基体中扩散出来的速度快于聚合物的降解速度。 Diffusion controlled release of the active substance diffusion from the matrix out faster than the rate of degradation of the polymer. 这种情况下活性物质将恒定地从基体中释放出来。 In this case a constant release of active substance from the matrix.

[0175] 作为第三种可行的作法,可以将活性物质引入多孔形状记忆塑性材料的孔中。 [0175] As a third possible approach, the active substance may be introduced into the pores of the porous shape memory plastic material. 在加入活性物质之后,关闭材料孔,然后将支架放置在上述有效位置处。 After addition of the active material, the material off the hole, and then the stent is placed at a position of said effective. 通过适当的外界刺激(加热或者光照射)打开孔,活性物质突然释放。 Through appropriate external stimuli (heat or light irradiation) to open the aperture, the sudden release of the active substance. 就这一应用而言,具有多种记忆形状的形状记忆塑性材料特别适合;这时,其中一种形状的作用是改变支架的形状,第二种形状的作用是打开孔。 On the applications, a variety of shape memory plastic material having shape memory particularly suitable; in this case, one effect is to change the shape of the shape of the stent, the effect of the shape of the second hole is open.

[0176] 如果将活性物质引入本发明支架的材料中,则活性物质的释放在支架植入后发生。 [0176] If the active substance of the present invention is incorporated in the scaffold material, the release of the active substance occurs after stent implantation. 活性物质的释放包含支架的降解;因此需要注意的是,活性物质从支架中扩散出来的速度必须低于支架材料的降解速度,而支架的机械稳定性并不受上述降解的影响。 Release of the active substance containing degradable stent; therefore should be noted that the active substance diffuses from the holder out speed must be below the degradation rate of the scaffold, and the mechanical stability of the stent is not affected by the above-described degradation.

[0177] 在所述实施方案中,支架可包括,例如多种S MP材料,例如一种用于保证支架的稳定性/牢固性的材料,以及一种涂布在支架表面并且含有活性物质的材料。 [0177] In the embodiment, the stent may comprise, for example, S MP various materials, such as a stent for the stability / robustness assurance material, and a coated stent surface and containing an active substance material.

[0178] 特别地,可进行以下应用: [0178] In particular, the following may be applied:

[0179] 髂骨支架 [0179] iliac stent

[0180] 这种支架的长度为10至120mm,通常为40至60mm。 [0180] The length of such stents is 10 to 120mm, usually from 40 to 60mm. 所述支架用于腹部区域。 The bracket for the abdominal region. 由于长形支架在使用时比较困难,故通常情况下使用两个支架。 Since the elongate support in the use of more difficult, so the use of two stents normally. 然而,由于本发明的支架具有柔韧性良好的特点,并且能够进行微创植入和移除,因此本发明的支架可以以现有技术认为根本不可行的长度来使用。 However, since the stent of the present invention has good flexibility characteristics, and is capable of minimally invasive implantation and removal, the stent of the present invention therefore may be considered in the prior art to use simply not feasible length.

[0181] 肾脏支架 [0181] Renal stent

[0182] 这时由于肾脏动脉的高弹性负载,要求较高的径向力,而较高的径向力又可能要求改善支架的机械加强。 [0182] In this case due to the high elastic load renal arteries, requires a higher radial force, while the high radial forces and may be required to improve the mechanical reinforcement bracket. 这种情况下“开槽管设计”或者使用涂布或包埋进SMP材料的常规支架均是适合的。 In this case, "slotted tube design" or with an applicator or package SMP material buried conventional stents were suitable. 两个实施方案中均能够使用对射线不透明的标记物(marker)。 Two embodiments can be used in both radiation-opaque marker (marker). 这时,确保导管球囊上支架的安全安装以及置入过程中的精确性更为重要。 In this case, make sure the catheter balloon and stent implantation process safe installation accuracy is more important. 由于生物的构造不同,需要有与之相适应的可变的长度及直径。 Since different biological structure, the need for a variable with suitable length and diameter. 而且,建议将远端防护装置与斑块过滤器(plaquefilter)结合使用。 Moreover, the proposed distal protection devices and plaque filter (plaquefilter) combination.

[0183] 颈动脉支架 [0183] Carotid Stent

[0184]-这种情况下可使用长形支架以避免前述将两个支架结合使用的技术。 [0184] - In this case you can use in order to avoid the aforementioned elongate support the technology used in combination with two stents.

[0185]-也可用在血管杈处 [0185] - also be used in blood vessels at the bifurcation

[0186]-可以优化调节为不同直径 [0186] - can be optimally adjusted to different diameters

[0187]-带有紧密网眼的网络是所希望的,亦是可行的(见上),因为为避免血液凝块进入大脑,可能需要过滤功能(斑块过滤功能) [0187] - with a tight mesh network is desired, is also possible (see above), because of the risk of blood clots into the brain, it may require filtering (plaque filtering)

[0188]-支架必须为压力稳定的,压力可能来自于外部,支架不应发生崩塌。 [0188] - Mounting pressure must be stable, the pressure may come from the outside, the stent should not occur collapse.

[0189] 股动脉支架(髋-膝) [0189] femoral artery stents (hip - knee)

[0190] 由于血管内的高弹性负载,要求较高的径向力,而较高的径向力又可能需要改善机械加强。 [0190] Due to the high elasticity of blood vessels load, requiring high radial force, and high radial force and may need to improve the mechanical reinforcement. 这种情况下“开槽管设计”是适合的(可通过使用常规框架),特别地可设想使用两个长形支架。 In this case, "slotted tube design" is suitable (through the use of conventional framework), in particular contemplated use two elongate support.

[0191] 冠状动脉支架 [0191] Coronary Stent

[0192]-金属丝线圈设计 [0192] - wire coil design

[0193]-不产生摩擦地无损伤引入是必不可少的条件,通过使用本发明的支架可以实现。 [0193] - without friction to no damage is an indispensable condition for the introduction, by the use of stents of the present invention may be implemented. _4] 非血■管支架设计 _4] Non-blood ■ pipe support design

[0195] 主要应用领域为整个胃肠道、气管及食管、胆管、输尿管、尿道以及输卵管。 [0195] The main application areas for the entire gastrointestinal tract, the trachea and esophagus, bile duct, ureter, urethra and fallopian tubes. 因此使用不同尺寸的支架。 Therefore, the use of different size stents. 在设计支架时必须单独考虑体液的不同pH值以及微生物的存在。 In the stent design must be considered separately when there are different pH values of body fluids and microorganisms.

[0196] 不论其使用位置如何,非血管支架主要用于体液,如胆汁、胰液或尿液的引流。 [0196] regardless of their position of use, non-vascular stents used in body fluids such as bile, pancreatic juice or urine drainage. 因此建议采用穿孔软管设计,一方面可以安全地将待排出的流体排出腔体,而另一方面可以通过整个管道吸收流体。 Therefore suggested perforated hose design, one can safely be discharged fluid discharge chamber, on the other hand can absorb the fluid through the entire pipeline. 而且,所使用的聚合物材料必须具有较高的柔韧性以保证佩戴舒适。 Furthermore, the polymer material used must have a high flexibility to ensure wearing comfort. 为了在X射线检测中更易于辨认,可以利用诸如硫酸钡的X射线造影物质遮蔽原料,或者将X射线不透明发色团通过,例如适当的单体聚合引入SMP材料。 In the X-ray detector in order to more easily recognizable, can be used such as barium sulfate X-ray contrast material shielding materials, or X-ray opaque chromophores by, for example, the introduction of appropriate monomers SMP material. 如果在存在微生物的区域内使用支架,则将抗生活性物质引入材料中可能是明智的。 If you use the stand in the presence of microorganisms within the region, will be the introduction of anti-life material material may be wise.

[0197] 尤其在尿道区频繁发生的支架结壳(encrustation)可以通过适当的涂层或表面改性减少。 [0197] In particular stent encrustation (encrustation) frequently occur in the urethral area can be reduced by a suitable coating or surface modification.

[0198] 支架的固定基本上取决于使用位置。 [0198] Fixation substantially depending on location. 就尿道支架而言,较近端位于肾盂内,较远端位于膀胱内或者体外。 On urethral stent, the near end is located within the pelvis, bladder or located more distal from the body. 扩张完成后,较近端在肾盂内形成环状,从而确保安全支撑。 After the expansion is complete, the closer the end to form a ring in the pelvis, so as to ensure the safety support.

[0199] 另一种固定支架的可行作法是通过向外的径向力将支架向外围组织紧压,或者支架包含用于固定的锚定元件(anchoring element)。 [0199] Another possible approach is through the mounting bracket outward radial force of the stent to the surrounding tissue pressed, or scaffold comprises anchoring element for fixing (anchoring element).

[0200] 就胆囊或肾脏支架而言,无损伤放置及移除是必不可少的条件。 [0200] to the gallbladder or kidney stent is placed and removed without injury is an indispensable condition. 特别地,必须确保在放置过程中组织不会由于摩擦而被损伤从而引发炎症。 In particular, it must ensure that the organization will not be damaged by friction causing inflammation during placement. 这一区域内所使用的支架没有任何可损伤组织的固定元件(retaining element)。 Fixing elements used in this region does not stand any damaged tissue (retaining element).

[0201] 实施例 [0201] Example

[0202] 现将例如适用于本发明的适合的材料作为实施例进行阐述: [0202] Now suitable material such as applicable to the present invention as described in Example:

[0203] 多嵌段共聚物实施例 [0203] Example multi-block copolymer

[0204] 多嵌段共聚物由基于十五内酯(TOL)及-己内酯(PCL)的大分子二醇以及二异氰酸制备。 [0204] The multi-block copolymer composed based pentadecanolide (TOL) and - Preparation of caprolactone (PCL) macroglycol and diisocyanate. PDL定义嵌段共聚物的十五内酯部分(不考虑二异氰酸酯桥连)及聚十五内酯片段的分子量。 PDL defined block copolymers pentadecanolide section (not considering diisocyanate bridging) molecular weight and poly pentadecanolide fragments. PCL定义单独的己内酯单元数据。 PCL define separate caprolactone unit data.

聚亚胺醋E-模量(7。 拉伸强 Polyimide vinegar E- modulus (tensile strength 7.

实施例PDL PCL Example PDL PCL implementation

分子量Mn C /MPa) 度(MPa) Molecular weight Mn C / MPa) degree (MPa)

100 Mfi % / 100 Mfi% /

1 192000 17 18 10000g/mol 1 192000 17 18 10000g / mol

22重量% / 78重量% / 22 wt% / 78 wt% /

2 120000 1,4 5 10000g/mol 10000g/mol 2 120000 1,4 5 10000g / mol 10000g / mol

41重量% / 59重量% / 41 wt% / 59 wt% /

3 196000 3 10 10000g/mol 10000g/mol 3 196000 3 10 10000g / mol 10000g / mol

[0205] 实施例8随温度变化的机械性能如下: [0205] Mechanical properties of Example 8 varies with temperature as follows:

[0206] 聚合物网络实施例 [0206] Polymer Network Example

[0207] 基于こ交酯单元及ロ-己内酯单元的大分子ニ甲基丙烯酸酯与丙烯酸正丁酯发生共聚反应,获得适合的聚合物网络。 [0207] ko-lactide based units and ro - n-butyl copolymerizable macromolecules caprolactone unit ni methacrylate and acrylic acid, obtaining suitable polymer network. こ交酯在大分子ニ甲基丙烯酸酯中的重量比为9重量% (或在实施例13中为11重量%)。 Ko lactide in Macromolecules ni methacrylate in a weight ratio of 9% by weight (Example 13 or 11% by weight). 大分子ニ甲基丙烯酸酯的分子量为约10000至11000g/mol。 Molecular weight molecules ni methacrylate is about 10,000 to 11000g / mol.

[0208] 无定形聚合物网络实施例 [0208] The amorphous polymer network Example

[0209] 无定形网络由ABA三嵌段ニ甲基丙烯酸酯制备,其中A代表聚(外消旋丙交酯)片段,B代表无规聚(环氧丙烷)片段(Mn = 4000g/mol)。 [0209] The amorphous network of ABA triblock methacrylic acid esters prepared Ni, wherein A represents a poly (rac-lactide) segment, B on behalf of random poly (propylene oxide) segment (Mn = 4000g / mol) . __ __

[0210] TO=多分散性 [0210] TO = Polydispersity

[0211] *DSC检测中发生聚合的样品 Samples polymerization occurs [0211] * DSC Testing

[0212] #数值高于100是由于杂质的存在 [0212] # 100 is higher than the value due to the presence of impurities

[0213] 检测聚合物无定形网络的其它热性能及机械性能。 [0213] Detection amorphous polymer networks of other thermal and mechanical properties. 检测结果合并于下表中。 Test results were combined in the following table.

[0214] *DMTA确定;nd——无法检测 [0214] * DMTA OK; nd-- undetectable

[0215] %2下的热转变 [0215] 2 under thermal transition%

[0216] 光敏性网络实施例 [0216] The photosensitive Network Example

[0217] 将IOmmol丙烯酸正丁酯(BA)、肉桂酸酯(0. l_3mmol)及约2mmol甲基丙烯酸轻こ酷(HEMA)在烧瓶中混合。 [0217] The IOmmol n-butyl acrylate (BA), cinnamic acid ester (0. l_3mmol) and approximately 2mmol methacrylic light ko cool (HEMA) were mixed in a flask. 混合物中加入Imol % AiBN及0. 3mol %聚(丙ニ醇)ニ甲基丙烯酸酯(Mn= 560)。 Imol% AiBN mixture was added 0. 3mol%, and poly (propyl alcohol Ni) Ni methacrylate (Mn = 560). 用注射器将混合物填满ー个带有两个甲基硅烷化载物架(objectcarrier)的模具,在所述两个载物架之间放入ー个厚度为0. 5mm的聚四氟こ烯树脂(Teflon)密封环。 The mixture with a syringe to fill ー months with two-silanated carrier rack (objectcarrier) mold, between the two carrier rack placed ー a thickness of 0. 5mm of polytetrafluoroethylene ko ene resin (Teflon) sealing ring. 混合物在80C下聚合18小时。 The mixture was polymerized at 80 C for 18 hours.

[0218] 其内发生交联的模具相当于永久模具。 [0218] crosslinking of the inner mold is a permanent mold. 混合物也可以其它任何形状进行交联。 The mixture may be any other shape cross-linked.

[0219] 聚合后将网络从模具中取出,并用150mL己烷馏分覆盖。 [0219] After polymerization network removed from the mold and cover with 150mL hexane fraction. 随后逐渐加入氯仿。 Followed by gradual addition of chloroform. 24小时内多次交换溶剂混合物以使低分子量的未交联组分溶出。 No more than one exchange crosslinking component solvent mixture within 24 hours to allow the dissolution of low molecular weight. 随后用己烷馏分清洗网络,并在30C下真空干燥过夜。 Then wash with hexane fraction networks and 30 C under vacuum overnight. 提取出的样品重量与先前重量的比即相当于凝胶的含量。 The extracted sample weight and the weight ratio is equivalent to the previous content of the gel. 以下两个表格表示出单体的用量及其在氯仿中的水份膨胀(moisture expansion)以及凝胶含量G。 The following table shows the amount of the two monomers and moisture expansion in chloroform (moisture expansion) and a gel content of G.

[0220] BA =丙烯酸丁酯;肉桂酸酷:CA =肉桂酸;HEMA =甲基丙烯酸轻こ酯;HEA =丙烯酸羟こ酯;HPMA =甲基丙烯酸羟丙酯;HPA =丙烯酸羟丙酯;PEGMA =聚(こニ醇)甲基丙稀Ife酷 [0220] BA = butyl acrylate; cinnamic acid cool: CA = cinnamic acid; HEMA = light ko methacrylic ester; HEA = hydroxyethyl acrylate ester ko; HPMA = hydroxypropyl methacrylate; HPA = hydroxypropyl acrylate; PEGMA = poly (ko ni alcohol), methyl acrylic Ife Cool

[0221] 在另外一系列实施例中,ニ元聚合物体系中再加入一部分2mmol甲基丙烯酸羟こ酷(HEMA),这是因为通过该共聚単体可以控制聚合物网络的机械性能。 [0221] In another series of embodiments, the polymer system Ni element was added portion 2mmol hydroxyethylmethacrylate ko cool (HEMA), this is because the body by radiolabeling the copolymer can be controlled mechanical properties of the polymer network.

[0222] 互穿网络IPN的制各 [0222] IPN IPN is prepared each

[0223] 如上所述,在0. I重量%的AiBN存在下,丙烯酸正丁酯与3重量% (0. 6mol% )的聚(丙ニ醇)ニ甲基丙烯酸酯(分子量560g/mol)发生交联。 [0223] As described above, at 0. I% by weight of AiBN presence, n-butyl acrylate and 3 wt% (0. 6mol%) of poly (acrylic Ni alcohol) ni methacrylate (molecular weight 560g / mol) crosslinking. 随后将膜泡(well)在THF中以溶出未用的単体,然后再干燥。 Then the bubble (well) THF dissolution radiolabeling body in order not to use, and then dried. 然后将膜泡在星形光反应活性大分子単体的THF溶液(10重量%)中,随后再干燥。 The membrane was then soaked in a star photoreactive active macromolecule radiolabeling body THF solution (10 wt%), followed by drying. 网络中加入的光反应活性组分为约30重量%。 Join the network light reactive group to about 30 percent by weight.

[0224] 星形光敏性大分子单体的制备 Preparation [0224] Star photosensitive macromer

[0225] 将四臂的星形聚(こニ醇)(分子量2000g/mol)溶于干燥的THF及三こ胺中。 [0225] The four-arm star poly (ko ni alcohol) (molecular weight of 2000g / mol) was dissolved in dry THF and three-ko amine. 为达到此目的,滴入缓慢溶于干燥THF的亚肉桂基こ酰氯。 For this purpose, in dry THF was slowly added dropwise alkylene ko cinnamyl chloride. 室温下搅拌反应混合物12小吋,然后在50C下搅拌3天。 The reaction mixture was stirred at room temperature for 12 inches, and then stirred at 50 C for 3 days. 滤去沉淀出的盐,滤液浓缩并用こ醚清洗产物。 The precipitated salt was filtered off, the filtrate was concentrated and the product was washed with ether ko. H-NMR测得转化率为85%。 H-NMR conversion ratio was 85%. UV分光光度仪显示,光反应前大分子单体的最大吸收在310nm处,光反应后最大吸收在254nm处。 UV spectrophotometer showed maximum absorption maximum absorption of light before the reaction of the macromonomers at 310nm, 254nm light at the reaction.

[0226] 检测聚合物无定形网络的其它热性能及机械性能。 [0226] Detection amorphous polymer networks of other thermal and mechanical properties. 检测结果合并于下表中。 Test results were combined in the following table.

[0227] *丙烯酸正丁酯网络;0. 3m0l%交联剂;无光反应活性组分 [0227] * n-butyl acrylate network;. 0 3m0l% crosslinking agent; matt reactive components

[0228] **IPN ;0. 6mol%交联剂,物理方法加入光反应活性组分 [0228] ** IPN;. 0 6mol% crosslinking agent, physically light reactive components added

[0229] 在循环光-机械实验中确定形状记忆性能。 [0229] In the cycle of light - to determine the mechanical properties of the shape memory experiments. 为达到此目的,使用厚度为0.5mm、长度为10mm、宽度为3mm的杠铃形冲压(punched-out)片。 For this purpose, a thickness of 0.5mm, a length of 10mm, a width of 3mm barbell shaped punched (punched-out) sheet.

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International ClassificationA61L27/50, A61F2/82, A61L31/18, A61L31/10, A61L31/14
Cooperative ClassificationA61F2/82, A61L31/10, A61L31/14, A61L31/18, A61L2400/16
European ClassificationA61F2/82, A61L31/18, A61L31/14, A61L31/10
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