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Publication numberCN105017538 A
Publication typeApplication
Application numberCN 201510205953
Publication dateNov 4, 2015
Filing dateApr 21, 2015
Priority dateApr 21, 2014
Publication number201510205953.6, CN 105017538 A, CN 105017538A, CN 201510205953, CN-A-105017538, CN105017538 A, CN105017538A, CN201510205953, CN201510205953.6
Inventors潘毅, 李兴建, 王亚茹, 郑朝晖, 丁小斌, 彭宇行
Applicant中国科学院成都有机化学有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Degradable shape memory high polymer material of regular network structure and preparation method therefor
CN 105017538 A
Abstract
The invention relates to a degradable shape memory high polymer material of a regular network structure and a preparation method therefor. The degradable shape memory high polymer material is characterized in that the degradable shape memory high polymer material of the regular network structure is obtained through step-growth polymerization of various equal-arm-length tetrahedral structure four-arm macromonomers with different special functional groups by utilizing an efficient click chemistry method. Different components of the network and compatibility and network soft and hard area distribution can be adjusted by selecting different four-arm macromonomers, so that the material has suitable microphase separation and different phase inversion temperatures to endow the shape memory performance. The preparation method can control the microstructure, shape memory performance, thermodynamic property and degradability of the material by adjusting the contents, types and molecular weights of the four-arm macromonomers, and is an effective method for obtaining the degradable shape memory high polymer material with excellent shape memory performance and high mechanical performance.
Claims(9)  translated from Chinese
1. 一种具有规整网络结构的可降解形状记忆高分子材料,采用四臂可降解大分子单体之间的点击化学反应获得具有规整网络结构的可降解形状记忆高分子材料,其特征在于可降解的规整网络结构具有形状记忆性能。 Biodegradable shape memory polymer A having a regular network structure, the use of click chemistry in four-arm degradable macromer is obtained between the biodegradable shape memory polymer material having a regular structure of the network, which can be characterized by degradation of regular network structure with shape memory properties.
2. 根据权利要求1所述的具有规整网络结构的可降解形状记忆高分子材料,其特征在于该高分子材料具有规整性网络结构,能够赋予材料优异的形状记忆性能包括快速的回复速度和高回复率。 The degradable shape memory polymer material having a regular network structure according to claim 1, characterized in that the polymer material having a network structure regularity, the material capable of imparting excellent shape memory properties including rapid response and high speed response rate.
3. 根据权利要求1所述的具有规整网络结构的可降解形状记忆高分子材料,其特征在于该高分子材料具有优异的机械性能和可降解性能。 3. The regular network structure having a shape memory biodegradable polymer material according to claim 1, characterized in that the polymer material has excellent mechanical properties and biodegradable properties.
4. 根据权利要求1所述的基于规整网络结构的可降解形状记忆高分子材料,其特征在于制备时原料配比为: A:四臂大分子单体(不同的官能团比为I : l)70-89wt% B :引发剂或催化剂0• I-Iwt % C :溶剂10% -30%。 4. Based on the regular network structure of biodegradable shape memory polymer according to claim 1, characterized in that the ratio of raw material preparation: A: four arms macromer (different functional groups ratio of I: l) 70-89wt% B: initiator or catalyst 0 • I-Iwt% C: 10% -30% solvent.
5. 根据权利要求1所述的具有规整网络结构的可降解形状记忆高分子材料,其特征在于其制备方法为:具有不同官能团的四臂大分子单体、催化剂或引发剂和溶剂按照一定的比例和顺序加入反应瓶中,室温下搅拌溶解,注入反应模具中,通过加热或光照反应一定的时间,脱模后室温干燥即可得到规整网络结构的形状记忆材料。 5. The regular network structure having a shape memory biodegradable polymer material according to claim 1, characterized in that the preparation method: four arms macromer having different functional groups, and a solvent catalyst or initiator in accordance with certain ratio and sequential addition reaction flask, stirred and dissolved at room temperature, the reaction injected into a mold, heating or light reaction by a certain time, after demolding and dried at room temperature to obtain a shape memory material regular network structure.
6. 根据权利要求4或5所述的基于规整网络结构的可降解形状记忆高分子材料,其特征在于选取可降解的四臂大分子单体,四臂大分子单体为四臂聚D,L-丙交酯、四臂聚己内酯、四臂聚十五内酯、四臂聚L-丙交酯、四臂聚乙交酯、四臂聚2-环氧己烷-1,5-二酮、四臂聚对二氧环己酮或它们之间的四臂二元共聚物或三元共聚物。 6. A network according to claim regular structure based biodegradable shape memory polymer according to 4 or 5, characterized in that the selected four-arm degradable macromer, macromer four arms of 4 - arm the D, L- lactide, polycaprolactone four arms, four arm poly pentadecanolide, four arm poly-L- lactide, polyglycolide four arms, four arm poly-2-epoxy-1,5-hexane - dione, four-arm polyethylene four-arm copolymers or terpolymers dioxanone or between them right.
7. 根据权利要求6所述的基于规整网络结构的可降解形状记忆高分子材料,其特征在于选取能够发生点击化学反应的官能化四臂大分子单体,四臂大分子单体为叠氮基封端的四臂大分子单体和炔基功能化的四臂大分子单体、巯基封端的四臂大分子单体和炔基或烯基功能化的四臂大分子单体、二烯(甲基呋喃)功能化四臂大分子单体和亲二烯体(顺丁烯二酸酐)功能化四臂大分子单体、四唑功能化的四臂大分子单体和烯基功能化的四臂大分子单体。 7. The regular network structure based biodegradable shape memory polymer according to claim 6, characterized in that the selected chemical reaction can occur Click-functionalized macromonomer four arms, four arms macromer azide four-terminated macromonomer arms and alkynyl groups functionalized macromonomer four arms, mercapto-terminated macromonomer and four arms alkenyl or alkynyl group of four arms functionalized macromers diene ( methyl furan) functionalized macromonomer four arms and dienophiles (maleic anhydride) functionalized macromonomer four arms, tetrazole functionalized macromonomer four arms and four alkenyl functional arm macromonomer.
8. 根据权利要求7所述的基于规整网络结构的可降解形状记忆高分子材料,其特征在于同一种功能化的四臂大分子单体可以是不同类型的一种、两种或多种大分子单体。 According to claim regular network structures based on biodegradable shape memory polymer materials, characterized in that said 7 on the same functional macromer of four arms may be of a different type, two or more large monomer molecule.
9. 根据权利要求5基于规整网络结构的可降解形状记忆高分子材料,其特征在于催化剂选用抗坏血酸钠还原CuS04、CuI、Cu(I) (PPh3)3Br ;引发剂选用偶氮类、有机过氧类热引发剂或光引发剂。 5 9. The regular network structure based on a shape memory polymer may be degradable claim, characterized in that the reduction catalyst is sodium ascorbate selected CuS04, CuI, Cu (I) (PPh3) 3Br; azo initiator chosen, the organic peroxide class thermal initiator or photoinitiator.
Description  translated from Chinese
规整网络结构的可降解形状记忆高分子材料及其制备方法 Regular network structure of biodegradable shape memory polymer material and its preparation method

技术领域 TECHNICAL FIELD

[0001] 本发明涉及具有规整网络结构的可降解形状记忆高分子材料的制备方法。 [0001] The present invention relates to a method for preparing regular network structure having shape memory biodegradable polymer materials. 将各种具有不同特殊官能团的四臂大分子单体经高效的点击化学方法交联得到规整网络结构的可降解形状记忆高分子材料,属于高分子新材料领域。 The four arms of various special macromer having different functional groups by efficient click chemistry crosslinking regular network structure of biodegradable shape memory polymer materials, belonging to the new field of polymer materials.

背景技术 Background technique

[0002] 形状记忆聚合物是一种可以响应外界刺激,并调整自身状态参数,从而回复到预先设定状态的一种智能高分子材料。 [0002] is a shape memory polymer can respond to external stimuli, and adjust its state parameters to return to the pre-set state an intelligent polymer materials. 它拥有刺激方式多样化、变形量大、性能和响应条件可调、易加工、赋形容易、质轻且价廉等特点,近年来成为智能高分子材料研究、开发和应用的一个新热点,在智能纺织材料、生物医用材料、航空航天技术、微流体控制技术和3D打印等领域显示了极为广阔的应用。 It has to stimulate diversification, large deformation, performance and response condition adjustable, easy processing, easy shaping, lightweight and inexpensive, etc., in recent years become a new hot spot intelligent polymer materials research, development and application, in the field of intelligent textile materials, biomedical materials, aerospace technology, microfluidic control technology and 3D printing show a very broad application.

[0003] 随着对形状记忆聚合物结构和性能认识的深化,以及高分子聚合物合成技术的发展,通过分子设计以得到预期结构和性能的形状记忆材料已成为现实。 [0003] As for the shape memory polymer structure and properties of the deepening of understanding and the development of polymer synthesis technology, designed to give the desired molecular structure and properties of shape memory material has become a reality. 材料能够展现形状记忆效应并不是某种聚合物的特殊性质,而是材料的结构和形态协同作用的结果。 Materials to show the shape memory effect is not the special nature of certain polymers, but the structure and morphology of the material results of synergy effects. 这就提供了一种可能,即把一些新的结构和形状记忆原理结合起来,通过分子设计及分子结构的调整来合成具有优异性能的形状记忆物材料。 This provides a possibility that some of the new structure and shape memory principle combined through molecular design and synthesis to adjust the molecular structure of a shape memory material with excellent properties. 丰富多彩的自然界为新型结构的发现与应用提供了很好的启示。 Colorful nature to discover and apply new structure provides a good inspiration.

[0004] 生物界经过20亿年的进化其结构与功能已达到几近完美的程度,实现了结构与功能和局部与整体的协调和统一。 [0004] After 20 billion years of biological evolution of its structure and function have reached near-perfect degree, and realize the structure and function of regional and global coordination and harmonization. 向自然学习已成为高性能材料发展的重要源泉,例如,仿生荷叶表面的超疏水自清洁涂层材料、仿生蜘蛛丝的"生物钢",仿生壁虎脚或贻贝的超粘性材料、仿生贝壳珍珠层的陶瓷增韧复合材料和仿生鲨鱼皮的游泳衣等。 To learn from nature has become an important source of the development of high-performance materials, such as lotus leaf surface biomimetic superhydrophobic self-cleaning coating materials, biomimetic spider silk "biological steel" bionic gecko feet or mussels super viscous materials, biomimetic shells toughened ceramic composites and biomimetic shark skin swimwear nacre. 利用仿生学设计先进功能材料已成为材料研究的前沿,并且成为材料设计的最高境界。 Bionic Design of Advanced Materials has become the forefront of materials research, and became the highest state of material design.

[0005] 海洋生物水母能对刺激做出迅速响应进而对海水能产生强的推动力,能够一张一弛地快速自由游动。 [0005] jellyfish marine organisms can respond quickly to a stimulus and then seawater can produce a strong impetus, a relaxation can quickly swim freely. 水母之所以能够对刺激做出快速、一致性响应的关键在于水母体内能够感受刺激的"起搏器"细胞在其肌肉中高度有序性排列并形成网络化所决定,这样水母能够实现刺激响应性在时空上的同步性进而能够做出快速响应和产生强的推动力。 Key jellyfish was able to respond quickly to stimuli, consistent response that jellyfish can feel the stimulation of "pacemaker" cells in their muscles height orderly arrangement and form a network of the decision, so that jellyfish can be achieved in response to stimuli sex in space and time synchronization and then be able to respond quickly and produce a strong driving force. 受此启发,我们设计制备了一种具有高度规整性网络结构的形状记忆高分子材料,使材料中够响应刺激的分子开关(可逆相)在材料网络结构中规整性的排列分布,实现刺激响应性在时空上的同步性,从而提高材料的形状记忆性能。 Inspired by this, we designed and fabricated a shape memory polymer material having a high degree of regularity network structure, and the material in response to stimulation enough molecular switch (reversible phase) material network structure regularity of the distribution arrangement to achieve the stimuli-responsive of synchronization in time and space, thereby improving the shape memory properties of the material. 由于形状记忆高分子材料的分子机理的本质是基于体系内部分子链构象变化的熵增原理。 Due to the nature of the molecular mechanism of shape memory polymer material it is based on the principle of entropy increase internal molecular system chain conformation change. 在一定温度下通过外力作用赋形,降低到转变温度(T trans)以下高分子的链段运动被冻结,从而阻止分子链的蜷曲,材料的形状得以固定;而在Ttrans以上,蜷曲分子的链段运动被激活,使其朝着最大构象熵的状态变化,材料得以回复。 At a certain temperature by forming an external force, reduced to a transition temperature (T trans) the following polymer segmental motion is frozen, thereby preventing the molecular chain flexed, the shape of the material to be fixed; whereas in Ttrans above, twist the molecular chain segmental motion is activated, so that the maximum toward the conformational entropy change of state, the material is recovered. 因此,为了获得链段运动的完全冻结,在T trans以下抑制分子链蜷曲以及在高于Ttrans时完全激活分子链,构建具有"高度规整性网络结构"分布的形状记忆网络是理想的方法。 Therefore, in order to obtain a complete freeze of segmental motion in the T trans molecular chain curled and less inhibition at higher Ttrans fully activated molecular chain, Build a "high degree of regularity network structure" shape memory network distribution is the ideal method. 因为利用规整网络结构能够有效地调节分子链间的相互作用力,使其在材料内部均匀分散,高分子链能够一致性的运动,并且均匀分布的分子开关(可逆相)能够在时空上一致性地快速传递外界的温度刺激,那么相应的高分子链段在Ttrans上下可以得到完全、快速的冻结与激活。 Because the use of regular network structure can effectively regulate the interaction between the molecular chains, uniformly dispersed within the material, the polymer chain can be consistent motion, and uniform distribution of molecular switch (reversible phase) can be consistent in time and space to stimulate the rapid transmission of the outside temperature, the corresponding polymer chain can be fully up and down in Ttrans quick freezing and activation. 因此,通过规整性网络结构的设计能够获得更优异的形状记忆性能。 Thus, by the regularity of the network structure is designed to be more excellent shape memory properties.

[0006] 另一方面,对于高度规整性网络结构形状记忆高分子材料,由于交联点分布很均匀、交联点之间分子链的长度相一致,在变形拉伸时,网络结构能够协同受力,内应力在不同高分子链上均匀分散,能够提高材料的机械性能。 [0006] On the other hand, the height of the regular network structure of a shape memory polymer, the crosslinking point is evenly distributed, the molecular chain length between the crosslinking points coincide, the tensile deformation, the structure of the network can be coordinated by force, internal stress is uniformly dispersed in different polymer chain can improve the mechanical properties of the material. 而无规交联的形状记忆聚合物,交联点密度分布不均匀、分子链长度不一致,在变形拉伸时高交联区域存在不可逆的分子链断裂, 不仅有损机械性能而且削弱形状记忆性能。 The random shape memory polymer crosslinked, the crosslink density of the uneven distribution of the molecular chain length is inconsistent, in the presence of high cross tensile deformation irreversible molecular chain-linked area, not only detrimental to the mechanical properties of the shape memory and impair performance . 因此,将高度规整性网络结构引入到形状记忆材料,不仅有利于提高形状记忆高分子材料的形状记忆性能,而且还可以增强材料的机械性能。 Thus, the highly structured network structure into the shape memory material, not only help to improve the shape memory effect of shape memory polymer materials, but also can enhance the mechanical properties of the material.

发明内容 SUMMARY

[0007] 本发明涉及具有规整网络结构的可降解形状记忆高分子材料及其制备方法。 [0007] The present invention relates to a biodegradable shape memory polymer material and method having regular network structure. 其特点是利用高效的点击化学方法可以将各种具有不同特殊官能团的等臂长四面体结构四臂大分子单体经过步增长聚合得到规整网络结构的可降解形状记忆高分子材料。 Which is characterized by the use of efficient Click chemistry can be a variety of arm length, etc. tetrahedral four-arm macromer having different functional groups through a special step-growth polymerization to obtain regular network structure of biodegradable shape memory polymer material. 通过分子结构的设计和调整,可以选择不同的四臂大分子单体来调整这些网络的不同组分及相容性、网络软硬区域分布,使其具有适当的微相分离和不同的相转变温度从而赋予形状记忆性能。 By designing and adjusting the molecular structure, can choose a different four-arm macromer to adjust various components and compatibility, network hardware and software distribution area of these networks, it has the appropriate micro-phase separation and different phase transition temperature thereby imparting shape memory properties. 该形状记忆聚合物根据四臂大分子单体官能团的不同使用不同的点击化学方法。 Depending on the shape memory polymer using a four-arm macromer functional groups different click chemistry. 该制备方法能通过调节四臂大分子单体的含量、种类和分子量来控制材料的微观结构、形状记忆性能、热力学性能和可降解性,是一种获得优异形状记忆性能和高机械性能的可降解形状记忆高分子材料的有效方法。 The preparation method by adjusting the content of the four-armed macromonomer type and molecular weight to control the microstructure of the material, the shape memory properties, thermal properties and biodegradability, is an acquired excellent shape memory properties and high mechanical properties can be effective way shape memory polymer degradation. 作为可降解形状记忆材料,本发明中涉及的形状记忆高分子材料尤其适用于生物医用材料领域,如支架材料、手术缝合线、药物控释和微创手术器件等。 As a biodegradable shape memory material, the shape memory polymer material of the present invention relates particularly useful in the field of biomedical materials, such as scaffolds, surgical sutures, drug delivery and minimally invasive surgical devices.

[0008] 本发明的目的在于提供一种利用高效的点击化学方法将各种具有不同特殊官能团的等臂长四面体结构四臂大分子单体经过步增长聚合制备规整网络结构的可降解形状记忆高分子材料的方法。 [0008] The object of the present invention is to provide an efficient use of click chemistry method has various arm length, etc. tetrahedral four-arm macromer different functional groups through special step growth polymerization regular network structure of biodegradable shape memory the method of polymer materials. 该发明通过高效、模块化的点击化学方法为构造规整网络结构的可降解形状记忆材料提供了一种通用的方法。 The invention, by effective, modular click chemistry methods for constructing regular network structure of biodegradable shape memory material provides a common approach. 可以通过简单调节四臂单分子单体的含量、 种类和分子量来控制材料的微观结构、形状记忆性能、热力学性能和可降解性,并因规整网络结构的高度规整性,可以获得优异形状记忆性能和高机械性能的可降解形状记忆高分子材料。 You can control the microstructure of the material by simply adjusting the four-arm single-molecule monomer content, type and molecular weight, shape memory properties, thermal properties and biodegradability, and a high degree of regularity, you can get excellent shape memory properties due to regular network structure and high mechanical properties of biodegradable shape memory polymer material.

[0009] 为达到上述目标,本发明提供了一种制备规整网络结构的可降解形状记忆高分子材料的方法:具有不同官能团的四臂大分子单体、催化剂或引发剂和溶剂按照一定的比例和顺序加入反应瓶中,室温下搅拌溶解,注入反应模具中。 [0009] To achieve the above object, the present invention provides a method for preparing regular network structure of a shape memory polymer may be degradable Method: macromonomer arms having four different functional groups, or a catalyst and a solvent in accordance with a certain proportion of initiator and sequentially added to the reaction flask, and dissolved with stirring at room temperature, the reaction injected into the mold. 通过加热或光照反应一定的时间,脱模后室温干燥即可得到规整网络结构的形状记忆材料。 Reaction by heating or light a certain time, after demolding and dried at room temperature to obtain a shape memory material regular network structure.

[0010] 本发明中规整网络结构的可降解形状记忆高分子材料的配比为: [0010] The present invention, the ratio of regular network structure of biodegradable shape memory polymer materials are as follows:

[0011] A:四臂大分子单体(不同的官能团比为I : l)70-89wt% [0011] A: four arms macromer (different functional groups ratio of I: l) 70-89wt%

[0012] B :引发剂或催化剂0 1-lwt%,C :溶剂10% -30% [0012] B: initiator or catalyst 0 1-lwt%, C: 10% -30% Solvent

[0013] 其中,在上述配比中: [0013] wherein, in the above ratio of:

[0014] A四臂大分子单体,选取可降解的具有不同官能团的四臂大分子单体,如四臂聚D,L-丙交酯、四臂聚己内酯、四臂聚十五内酯、四臂聚L-丙交酯、四臂聚乙交酯、四臂聚2-环氧己烷-1,5-二酮、四臂聚对二氧环己酮、四臂二元共聚物或三元共聚物等单体的一种或多种。 [0014] A four-arm macromer, select four-arm biodegradable macromer having different functional groups, such as the four-arm poly-D, L- lactide, polycaprolactone four arms, four arm poly fifteen lactones, four-arm poly-L- lactide, polyglycolide four arms, four arm poly-2 ethylene hexane-1,5-dione, four arm poly dioxanone, four arms two yuan a copolymer or terpolymer of one or more monomers.

[0015] B四臂大分子单体的末端官能基团,选取能够发生点击化学反应的官能基团,如叠氮基封端的四臂大分子单体和炔基功能化的四臂大分子单体、巯基封端的四臂大分子单体和炔基或烯基功能化的四臂大分子单体、二烯(甲基呋喃)功能化四臂大分子单体和亲二烯体(顺丁烯二酸酐)功能化四臂大分子单体、四唑功能化的四臂大分子单体和烯基功能化的四臂大分子单体等。 [0015] terminal functional groups B four arms macromonomer, click to select the chemical reaction can occur a functional group such as azide-terminated macromonomer four arms and four alkyne group functionalized macromolecules single arm body, thiol-terminated macromonomer four arms and alkynyl or alkenyl functionalized macromonomer four arms, diene (methyl furan) functionalized macromonomer four arms and dienophiles (maleic anhydride) functionalized macromonomer four arms, tetrazole functionalized macromonomer four arms and alkenyl functional four-arm macromolecular monomer.

[0016] C引发剂或催化剂,催化剂选用抗坏血酸钠还原CuSO4体系、CuI、Cu⑴(PPh 3) 3Br 等;引发剂选用偶氮类或有机过氧类引发剂或各种光引发剂。 [0016] C initiator or catalyst, a catalyst selected sodium ascorbate reduction CuSO4 system, CuI, Cu⑴ (PPh 3) 3Br the like; azo initiator or an organic peroxide selected initiators or various photoinitiators.

[0017] D溶剂,选取能促进A、B和C的分散而加入适量的溶剂,要求毒性小,溶解性好。 [0017] D solvent selected to promote A, B C and the dispersion and adding an appropriate amount of solvent required low toxicity, good solubility.

[0018] 为了制备形状记忆材料,主要通过改变B构成的聚合物的玻璃化温度、熔点和分子量来获得一系列形状记忆性能的高分子材料。 [0018] In order to prepare a shape memory material, mainly by changing the polymer has a glass transition temperature, melting point and molecular weight of B formed to obtain a series of shape-memory properties of polymer materials.

具体实施方式 detailed description

[0019] 下面结合实施例对本发明作进一步的描述。 [0019] The following combination of embodiments of the present invention will be further described. 本发明所涉及的主题范围并非仅限于这6个实例,而应以权利要求中限定的为准。 Relating to the scope of the invention is not limited to these six instances, but should be defined in the claims shall prevail.

[0020] 实例1 [0020] Example 1

[0021] A四臂大分子单体 [0021] A four-arm macromer

[0022] 叠氮基功能化四臂聚D,L-丙交酯(Mn= 23000) 3g [0022] azido-functionalized four arm poly D, L- lactide (Mn = 23000) 3g

[0023] 端炔基功能化四臂聚D,L-丙交酯(Mn= 23000) 3g [0023] terminal alkyne group functionalized four arm poly D, L- lactide (Mn = 23000) 3g

[0024] B催化剂 [0024] B catalyst

[0025] CuI 0. 06g [0025] CuI 0. 06g

[0026] C 溶剂 [0026] C solvent

[0027] 二氯甲烷48g [0027] 48g of dichloromethane

[0028] 反应式如下: [0028] The reaction is as follows:

[00291 [00291

Figure CN105017538AD00051

[0030] 其制备方法为:叠氮基和端炔基功能化四臂大分子单体、CuI和二氯甲烷加入反应瓶中,室温下搅拌溶解,注入反应模具中。 [0030] The preparation process: azido and alkyne end group functionalized macromonomer four arms, CuI and dichloromethane added to the reaction flask, and dissolved with stirring at room temperature, the reaction injection mold. 在60C条件下反应6-12小时,脱模后干燥即可得到规整网络结构的形状记忆材料。 The reaction for 6-12 hours at 60 C conditions, drying can be obtained after releasing a shape memory material regular network structure.

[0031] 产物指标: [0031] The product index:

[0032] 玻璃化转变温度:46C ; [0032] The glass transition temperature: 46 C;

[0033] 51C下的形状恢复率:99% ; Shape recovery ratio [0033] 51 C under: 99%;

[0034] 形状恢复时间:5秒。 [0034] The shape recovery time: 5 seconds.

[0035] 实例2 [0035] Example 2

[0036] A四臂大分子单体 [0036] A four-arm macromer

[0037] 巯基功能化四臂聚己内酯(Mn= 46000) 3g [0037] mercapto functional four-arm polycaprolactone (Mn = 46000) 3g

[0038] 降冰片烯功能化四臂聚己内酯(Mn= 46000) 3g [0038] norbornene functional four-arm polycaprolactone (Mn = 46000) 3g

[0039] B催化剂 [0039] B catalyst

[0040] 光引发剂(2-羟基-4' -(2-羟基乙氧基)-2-甲基苯丙酮)0.06g [0040] photoinitiator (2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone) 0.06 g of

[0041] C 溶剂 [0041] C solvent

[0042] 二氯甲烷48g [0042] 48g of dichloromethane

[0043] 反应式如下: [0043] reaction is as follows:

Figure CN105017538AD00061

[0045] 其制备方法为:巯基和降冰片烯功能化四臂大分子单体、光引发剂和二氯甲烷加入反应瓶中,室温下搅拌溶解,注入反应模具中。 [0045] The preparation process: a mercapto group and norbornene functionalized four arms macromers, a photoinitiator and dichloromethane added to the reaction flask, and dissolved with stirring at room temperature, the reaction injection mold. 在室温条件下紫外光照反应1-10分钟,脱模后干燥即可得到规整网络结构的形状记忆材料。 UV irradiation for 1-10 minutes at room temperature, dried to obtain the release of shape memory material regular network structure.

[0046] 产物指标: [0046] The product index:

[0047] 熔点:54C ; [0047] Melting point: 54 C;

[0048] 70C下的形状恢复率:99% ; Shape recovery ratio [0048] 70 C under: 99%;

[0049] 形状恢复时间:11秒。 [0049] Shape Recovery time: 11 seconds.

[0050] 实例3 [0050] Example 3

[0051] A四臂大分子单体 [0051] A four-arm macromer

[0052] 甲基咲喃功能化四臂聚丙交酯-Co-己内酯(Mn= 10500) 3g [0052] methyl Kou Nan functional four-arm polylactide -Co- caprolactone (Mn = 10500) 3g

[0053] 顺丁烯二酸酐功能化四臂聚丙交酯-Co-己内酯(Mn= 10500) 3g [0053] Maleic anhydride functional four-arm polylactide -Co- caprolactone (Mn = 10500) 3g

[0054] B催化剂 [0054] B catalyst

[0055] 光引发剂(2-羟基-4' -(2-羟基乙氧基)-2-甲基苯丙酮) 0.06g [0055] The photoinitiator (2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone) 0.06 g of

[0056] C 溶剂 [0056] C solvent

[0057] 二氯甲烷48g [0057] 48g of dichloromethane

[0058] 反应式如下: [0058] The reaction is as follows:

Figure CN105017538AD00062

[0060] 其制备方法为:甲基呋喃和顺丁烯二酸酐功能化四臂聚丙交酯-CO-己内酯、光引发剂和二氯甲烷加入反应瓶中,室温下搅拌溶解,注入反应模具中。 [0060] The preparation process: methyl furan and maleic anhydride functional four-arm polylactide -CO- caprolactone, photoinitiator and dichloromethane added to the reaction flask, stirred and dissolved at room temperature, the reaction injection mold in. 在37C条件下反应6-12小时,脱模后干燥即可得到规整网络结构的形状记忆材料。 The reaction 6-12 hours at 37 C conditions, drying can be obtained after releasing a shape memory material regular network structure.

[0061] 产物指标: [0061] The product index:

[0062] 玻璃化转变温度:36C ; [0062] Glass transition temperature: 36 C;

[0063] 40C下的形状恢复率:99% ; Shape recovery ratio [0063] 40 C under: 99%;

[0064] 形状恢复时间:14秒。 [0064] Shape Recovery time: 14 seconds.

[0065] 实例4 [0065] Example 4

[0066] A四臂大分子单体 [0066] A four-arm macromer

[0067] 双键功能化四臂聚丙交酯-co-2-环氧己烷-1,5-二酮(Mn = 10000) 3g [0067] double function of the four-arm polylactide -co-2- epoxy hexane-1,5-dione (Mn = 10000) 3g

[0068] 四唑功能化四臂聚丙交酯-co-2-不氧己烷-1,5-二酮(Mn = 10000) 2g [0068] tetrazol-functional four-arm polylactide not -co-2- oxo-hexane-1,5-dione (Mn = 10000) 2g

[0069] 四唑功能化四臂聚己内酯(Mn = 10000) Ig [0069] tetrazol-functional four-arm polycaprolactone (Mn = 10000) Ig

[0070] B引发剂 [0070] B initiator

[0071] 无引发剂 [0071] No initiator

[0072] C 溶剂 [0072] C solvent

[0073] 二氯甲烷48g [0073] 48g of dichloromethane

[0074] 反应式如下: [0074] reaction is as follows:

Figure CN105017538AD00071

[0076] 其制备方法为:双键和四唑功能化功能化四臂聚丙交酯-co-2-环氧己烷-1,5-二酮、四唑功能化四臂聚己内酯、二氯甲烷加入反应瓶中,室温下搅拌溶解,注入反应模具中。 [0076] The preparation process: a double bond and tetrazole functional features of the four-arm polylactide -co-2- epoxy hexane-1,5-dione, tetrazolyl functional four-arm polycaprolactone, the reaction flask was added methylene chloride, stirred and dissolved at room temperature, the reaction injected into the mold. 在室温条件下紫外光照反应1-10分钟,脱模后干燥即可得到规整网络结构的形状记忆材料。 UV irradiation for 1-10 minutes at room temperature, dried to obtain the release of shape memory material regular network structure.

[0077] 该材料具有形状记忆性能,主要产物指标如下: [0077] The material has shape memory properties, the main product indicators are as follows:

[0078] 玻璃花转变温度:38C ; [0078] Glass transition temperature Flowers: 38 C;

[0079] 38C下的形状恢复率:99% ; Shape recovery ratio [0079] 38 C under: 99%;

[0080] 形状恢复时间:8秒。 [0080] Shape Recovery time: 8 seconds.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
CN101475677A *Dec 18, 2008Jul 8, 2009浙江大学Multi-block biodegradable shape memory polymeric compound with regular structure and preparation thereof
US6388043 *Feb 23, 1999May 14, 2002Mnemoscience GmbhShape memory polymers
Non-Patent Citations
Reference
1 *THOMAS DEFIZE等: ""Multifunctional Polye-caprolactone)-Forming Networks by Diels-Alder Cycloaddition:Effect of the Adduct on the Shape-Memory Properties"", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》
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Classifications
International ClassificationC08G81/00
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