CN103936938A - Photoinduced shape memory high polymer based on host and guest actions and preparation method thereof - Google Patents
Photoinduced shape memory high polymer based on host and guest actions and preparation method thereof Download PDFInfo
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Abstract
本发明公开一种以光控主客体作用作为可控“交联/解交联”官能团的形状记忆高分子材料及其制备方法。在结构设计时，将主客体功能单体同时修饰到高分子基体材料中，其中环糊精作为主体分子，偶氮苯作为客体分子。当偶氮苯以反式结构存在时，与环糊精发生分子识别，通过主客体相互作用，形成稳定的包合物，得到“交联”结构。这时在高温条件下，对高分子材料施加外力，进行赋形，获得临时形状。当用350纳米以下波长光源进行照射时，偶氮苯从反式结构转变为顺式结构，顺式偶氮苯与环糊精之间不能发生分子识别作用，主客体作用被破坏，这时包合物被拆散，得到“解交联”结构。这时材料的形状发生回复，获得初始形状，从而实现材料的形状记忆功能。The invention discloses a shape-memory macromolecule material and a preparation method thereof with light-controlled host-guest interaction as a controllable "crosslinking/decrosslinking" functional group. When designing the structure, the host and guest functional monomers are simultaneously modified into the polymer matrix material, with cyclodextrin as the host molecule and azobenzene as the guest molecule. When azobenzene exists in the trans structure, molecular recognition occurs with cyclodextrin, and a stable clathrate is formed through host-guest interaction, resulting in a "cross-linked" structure. At this time, under high temperature conditions, an external force is applied to the polymer material to shape it and obtain a temporary shape. When irradiated with a light source with a wavelength below 350 nanometers, the azobenzene changes from a trans structure to a cis structure, and molecular recognition cannot occur between cis-azobenzene and cyclodextrin, and the host-guest interaction is destroyed. The compound is disassembled to obtain a "decrosslinked" structure. At this time, the shape of the material is recovered and the original shape is obtained, thereby realizing the shape memory function of the material.
Description
技术领域technical field
本发明涉及一种光致形状记忆高分子材料及其制备方法，属于智能高分子材料领域。The invention relates to a photoinduced shape memory polymer material and a preparation method thereof, belonging to the field of intelligent polymer materials.
背景技术Background technique
形状记忆高分子材料是一种重要的智能材料，与其他类型形状记忆材料相比，具有柔韧性好、重量轻、价格便宜和易加工性等优点，在生物医用材料、航空航天材料、智能器件材料、光电信息材料等领域具有重要的应用前景，因此受到研究者的广泛关注。形状记忆高分子材料是指能对外界刺激做出响应，并对材料形状进行调整，很快回复到预先设计形状的高分子材料。根据响应方式的不同，形状记忆高分子材料为热致型、光致型、酸碱型、磁致型、电致型等类型。Shape memory polymer material is an important smart material. Compared with other types of shape memory materials, it has the advantages of good flexibility, light weight, low price and easy processing. It is used in biomedical materials, aerospace materials, smart devices, etc. Materials, optoelectronic information materials and other fields have important application prospects, so they are widely concerned by researchers. Shape memory polymer materials refer to polymer materials that can respond to external stimuli, adjust the shape of the material, and quickly return to the pre-designed shape. According to the different response modes, the shape memory polymer materials are thermotropic, phototropic, acid-base, magnetotropic, electrotropic and other types.
在各种类型形状记忆高分子材料中，热致型记忆材料得到广泛、系统研究，但是在许多情况下，如：生物体内形状记忆材料、人工肌肉、恒温环境的变形等领域，由于对温度敏感，热致型形状记忆材料的应用受到限制。在这些领域中，光致形状记忆高分子材料具有独特优势。而且，光作为刺激源，具有非接触性、瞬时性、定点性和清洁性等特点，所以光致形状记忆高分子材料特别适合于对热敏感的场所，并且能够实现远程控制和定点控制。Among various types of shape memory polymer materials, thermotropic memory materials have been widely and systematically studied, but in many cases, such as: shape memory materials in vivo, artificial muscles, deformation of constant temperature environment, etc. , the application of thermotropic shape memory materials is limited. In these fields, photoinduced shape memory polymer materials have unique advantages. Moreover, as a stimulus source, light has the characteristics of non-contact, transient, fixed-point and cleanliness, so photoinduced shape-memory polymer materials are especially suitable for heat-sensitive places, and can realize remote control and fixed-point control.
当前研究较多的光致形状记忆高分子材料主要是在热致记忆高分子体系中引入光热转换材料，通过光照辐射产生热，诱导材料发生相应的形状变化，其记忆本质与热致形状记忆高分子材料相同。这类材料可以实现远程控制，但仍然会使材料体系产生热量，在恒温体系中应用时受到制约，同时由于光照生热后，热量在材料中进行传导，无法实现定点控制。为克服这些缺陷，研究者将具有可控“交联/解交联”特性的肉桂酸基团引入形状记忆高分子材料中，获得了光控的形状记忆高分子(Nature,2005,434:879；Biomacromolecules,2011,12:235)。肉桂酸基团对260纳米的紫外光敏感，当赋形同时用大于260纳米波长光照射时，肉桂酸生成二聚体，发生交联，材料形变被固定；当用小于260纳米波长光照射时，交联结构打开，材料形状得到回复。这个体系克服了光照变形过程中热量的产生，但是激发肉桂酸基团，所需紫外光波长短，相应能量要求较高。The photoinduced shape memory polymer materials that are currently studied are mainly the introduction of photothermal conversion materials into the thermal memory polymer system, which generates heat through light radiation, and induces corresponding shape changes in the material. The memory essence is the same as thermal shape memory Polymer materials are the same. This kind of material can realize remote control, but it will still generate heat in the material system, which is restricted when used in a constant temperature system. At the same time, due to the heat generated by light, the heat is conducted in the material, and fixed-point control cannot be realized. In order to overcome these defects, researchers introduced cinnamic acid groups with controllable "crosslinking/uncrosslinking" characteristics into shape memory polymer materials, and obtained light-controlled shape memory polymers (Nature, 2005, 434:879 ; Biomacromolecules, 2011, 12:235). The cinnamic acid group is sensitive to ultraviolet light at 260 nanometers. When the shape is irradiated with light with a wavelength greater than 260 nanometers, cinnamic acid will form a dimer, cross-link, and the deformation of the material will be fixed; when irradiated with light with a wavelength of less than 260 nanometers , the cross-linked structure is opened, and the shape of the material is restored. This system overcomes the generation of heat during the light deformation process, but the excitation of cinnamic acid groups requires short wavelengths of ultraviolet light and relatively high energy requirements.
主客体作用具有选择性，而且相互作用力强。通过主客体作用，主体分子和客体分子之间能形成稳定的包合物。环糊精和偶氮苯是一类重要的光控主客体分子对，其中环糊精是主体分子，偶氮苯是客体分子。偶氮苯处于反式结构时，通过主客体作用与环糊精发生分子识别，形成稳定的包合物；当用350纳米光照射后，偶氮苯从反式结构转变为顺式结构，与环糊精之间不能发生分子识别，包合物结构被破坏。因此，环糊精和偶氮苯之间也是一种具有可控“交联/解交联”的官能团，而且350纳米波长光源可将其激发，实现光控的可逆交联作用，所需能量要求低，激发效率高。The host-guest effect is selective and the interaction force is strong. Through the host-guest interaction, a stable clathrate can be formed between the host molecule and the guest molecule. Cyclodextrin and azobenzene are an important class of light-controlled host-guest molecule pairs, in which cyclodextrin is the host molecule and azobenzene is the guest molecule. When azobenzene is in the trans structure, molecular recognition occurs with cyclodextrin through host-guest interaction to form a stable clathrate; when irradiated with 350nm light, azobenzene changes from trans structure to cis structure, and Molecular recognition cannot occur between cyclodextrins, and the clathrate structure is destroyed. Therefore, between cyclodextrin and azobenzene is also a functional group with controllable "crosslinking/decrosslinking", and a light source with a wavelength of 350 nanometers can excite it to achieve light-controlled reversible crosslinking. Low requirements, high excitation efficiency.
发明内容Contents of the invention
针对目前形状记忆高分子材料的缺点，本发明的目的是提供一种基于主客体作用的光控形状记忆高分子材料，同时本发明也提供这种形状记忆高分子材料的制备方法。In view of the shortcomings of the current shape memory polymer materials, the purpose of the present invention is to provide a light-controlled shape memory polymer material based on host-guest interaction, and at the same time, the invention also provides a preparation method for the shape memory polymer material.
为了达到上述目的，本发明采用以下的技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明所述的一种基于主客体作用的光致形状记忆高分子及其制备方法，其制备过程是将20-70wt％双键修饰的环糊精单体、30-80wt％双键修饰的偶氮苯单体、2-25wt％交联剂、10-60wt％功能单体、0.5-3wt％引发剂混合均匀，通氮气1小时后将混合体系转入模具，密封后，升温到60-130℃反应3-8小时，再升温到160℃反应1-3小时，冷却到室温后打开模具，即得到基于主客体作用的光致形状记忆高分子。A photoinduced shape memory polymer based on host-guest interaction and its preparation method according to the present invention, the preparation process is 20-70wt% double bond modified cyclodextrin monomer, 30-80wt% double bond modified Azobenzene monomer, 2-25wt% cross-linking agent, 10-60wt% functional monomer, 0.5-3wt% initiator are mixed evenly, and the mixed system is transferred to the mold after 1 hour of nitrogen gas, and after sealing, the temperature is raised to 60- React at 130°C for 3-8 hours, then raise the temperature to 160°C for 1-3 hours, cool to room temperature and open the mold to obtain a photoinduced shape memory polymer based on host-guest interaction.
本发明所述的双键修饰的环糊精单体为α-环糊精单体或β-环糊精单体，通过丙烯酰氯、甲基丙烯酰氯、丙烯酸、甲基丙烯酸、丙烯酰胺等单体中的一种与α-环糊精或β-环糊精反应制得。The cyclodextrin monomer modified by the double bond in the present invention is an α-cyclodextrin monomer or a β-cyclodextrin monomer, which can be obtained by acryloyl chloride, methacryloyl chloride, acrylic acid, methacrylic acid, acrylamide, etc. One of the bodies reacts with α-cyclodextrin or β-cyclodextrin.
本发明所述的双键修饰的偶氮苯单体通过丙烯酰氯、甲基丙烯酰氯、丙烯酸、甲基丙烯酸等单体中的一种与对羟基偶氮苯或对氨基偶氮苯反应制得。The double bond modified azobenzene monomer of the present invention is prepared by reacting one of acryloyl chloride, methacryloyl chloride, acrylic acid, methacrylic acid and other monomers with p-hydroxyazobenzene or p-aminoazobenzene .
本发明所述的交联剂选自二乙烯基苯、N,N-亚甲基双丙烯酰胺，乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、聚丙二醇二甲基丙烯酸酯、聚己内酯二甲基丙烯酸酯中的一种或几种。The crosslinking agent described in the present invention is selected from divinylbenzene, N,N-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethyl One or more of acrylate and polycaprolactone dimethacrylate.
本发明所述的功能单体选自甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸缩水甘油酯、丙烯酸、甲基丙烯酸、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基羟乙酯、N-乙烯吡咯烷酮中的一种或几种。The functional monomer described in the present invention is selected from methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, acrylic acid-2-hydroxyl One or more of ethyl ester, 2-hydroxyethyl methacrylate, and N-vinylpyrrolidone.
本发明所述的引发剂选自偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、二叔丁基过氧化物中的一种或几种。The initiator described in the present invention is selected from one or more of azobisisobutyronitrile, azobisisoheptanonitrile, dibenzoyl peroxide and di-tert-butyl peroxide.
本发明所述的光致形状记忆高分子的形状记忆过程是通过光控的环糊精与偶氮苯之间的可逆交联作用来实现，当偶氮苯处于反式结构时，与环糊精通过分子识别作用形成包合物，获得交联结构，经350纳米光照射后，偶氮苯转变为顺式结构，与环糊精的分子识别作用被破坏，得到解交联结构。The shape memory process of the photoinduced shape memory polymer of the present invention is realized by the reversible cross-linking between the light-controlled cyclodextrin and azobenzene. When the azobenzene is in the trans structure, the cyclodextrin The azobenzene forms an inclusion compound through molecular recognition and obtains a cross-linked structure. After being irradiated with 350nm light, the azobenzene transforms into a cis structure, and the molecular recognition with cyclodextrin is destroyed, and a de-crosslinked structure is obtained.
本发明所述的形状记忆过程中的赋形和回复过程是，将不同模具中获得的记忆高分子材料升温到30-180℃下赋形，接着冷却到室温，得到赋形的临时形状，将该材料用小于350纳米波长的光源照射，材料的形状即发生回复，实现光致形状记忆过程。The shaping and recovery process in the shape memory process of the present invention is that the temperature of the memory polymer material obtained in different molds is raised to 30-180°C for shaping, and then cooled to room temperature to obtain a shaped temporary shape. The material is irradiated with a light source with a wavelength of less than 350 nanometers, and the shape of the material is restored, realizing the photoinduced shape memory process.
本发明的优点是：The advantages of the present invention are:
(1)光致形状记忆高分子材料的制备方法简单，而且制备方法具有很强的通用行的特点，通过选择不同的主客体分子单体、功能单体，可以得到性能各异的各种光致形状记忆高分子材料；(1) The preparation method of photoinduced shape memory polymer materials is simple, and the preparation method has strong general characteristics. By selecting different host-guest molecular monomers and functional monomers, various optical materials with different properties can be obtained. Shape memory polymer materials;
(2)用350纳米波长光源即可对材料进行激发变形，所需要能量低；(2) The material can be excited and deformed with a 350nm wavelength light source, and the energy required is low;
(3)本方法所制备的形状记忆材料，可以实现多次的赋形和回复过程；(3) The shape memory material prepared by this method can realize multiple shaping and recovery processes;
(4)在材料的特定部位，通过350纳米光源定点照射，能够实现材料指定部位的形状回复，从而实现对变形过程的定点控制；(4) At a specific part of the material, the shape recovery of the designated part of the material can be realized through fixed-point irradiation of a 350-nanometer light source, thereby realizing fixed-point control of the deformation process;
具体实施方式Detailed ways
下面结合实施例来描述本发明的具体实施方式，但本发明不只局限于以下实施例。The specific implementation of the present invention will be described below in conjunction with the examples, but the present invention is not limited to the following examples.
实施例1Example 1
将α-环糊精6.5g、甲基丙烯酰氯1.2g和三乙胺0.5g溶于150mL的N,N-二甲基甲酰胺中，室温反应4小时，倒入甲醇溶液中，将沉淀烘干，得到双键修饰的α-环糊精单体。Dissolve 6.5g of α-cyclodextrin, 1.2g of methacryloyl chloride and 0.5g of triethylamine in 150mL of N,N-dimethylformamide, react at room temperature for 4 hours, pour into methanol solution, and dry the precipitate Dry to obtain double bond modified α-cyclodextrin monomer.
实施例2Example 2
将对氨基偶氮苯5.5g、丙烯酰氯2.8g和三乙胺1.2g溶于100mL的N,N-二甲基甲酰胺中，室温反应6小时，倒入水中，将沉淀烘干，得到双键修饰的偶氮苯单体。Dissolve 5.5 g of p-aminoazobenzene, 2.8 g of acryloyl chloride and 1.2 g of triethylamine in 100 mL of N,N-dimethylformamide, react at room temperature for 6 hours, pour into water, and dry the precipitate to obtain bis Bond-modified azobenzene monomer.
实施例3Example 3
将α-环糊精单体5.8g、偶氮苯单体2.1g、N,N-亚甲基双丙烯酰胺1.8g、甲基丙烯酸丁酯1.6g和偶氮二异丁腈0.1g混合均匀，通氮气1小时后将混合体系转入模具，密封后，升温到75℃反应6小时，再升温到160℃反应1小时，冷却到室温后打开模具，即得到基于主客体作用的光致形状记忆高分子材料。Mix 5.8g of α-cyclodextrin monomer, 2.1g of azobenzene monomer, 1.8g of N,N-methylenebisacrylamide, 1.6g of butyl methacrylate and 0.1g of azobisisobutyronitrile After 1 hour of blowing nitrogen, transfer the mixed system into the mold. After sealing, raise the temperature to 75°C for 6 hours, and then raise the temperature to 160°C for 1 hour. After cooling to room temperature, open the mold to obtain the photoinduced shape based on the interaction of host and guest. Memory polymer materials.
实施例4Example 4
将β-环糊精单体10.2g、偶氮苯单体3.8g、二乙烯基苯2.6mLg、甲基丙烯酸-2-羟基羟乙酯3.2mL和过氧化二苯甲酰0.25g混合均匀，通氮气1小时后将混合体系转入模具，密封后，升温到80℃反应4小时，再升温到160℃反应2小时，冷却到室温后打开模具，即得到基于主客体作用的光致形状记忆高分子材料。Mix 10.2g of β-cyclodextrin monomer, 3.8g of azobenzene monomer, 2.6mL of divinylbenzene, 3.2mL of 2-hydroxyethyl methacrylate and 0.25g of dibenzoyl peroxide, After blowing nitrogen for 1 hour, transfer the mixed system into the mold. After sealing, raise the temperature to 80°C and react for 4 hours, then raise the temperature to 160°C and react for 2 hours. After cooling to room temperature, open the mold to obtain the photoinduced shape memory based on the host-guest interaction. Polymer Materials.
实施例5Example 5
将具有初始形状的形状记忆高分子材料加热到120℃，赋形后快速冷却到室温，获得临时形状。然后用小于350纳米波长的光源对材料进行照射，材料形状逐渐回复到初始形状，实现光致形状记忆过程。The shape-memory polymer material with the initial shape is heated to 120°C, and then rapidly cooled to room temperature after shaping to obtain a temporary shape. Then, the material is irradiated with a light source with a wavelength of less than 350 nanometers, and the shape of the material gradually returns to the original shape, realizing the photoinduced shape memory process.
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| CN108484832A (en) * | 2018-04-17 | 2018-09-04 | 西北大学 | A kind of preparation method with the self-healing hydrogel ultraviolet, pH is sensitive |
| CN108484832B (en) * | 2018-04-17 | 2020-10-16 | 西北大学 | Preparation method of self-healing hydrogel with ultraviolet and pH sensitivity |
| CN108948265A (en) * | 2018-07-23 | 2018-12-07 | 金陵科技学院 | A kind of nano-carrier and preparation method thereof with photoresponse |
| CN109134748A (en) * | 2018-07-23 | 2019-01-04 | 金陵科技学院 | One kind can functionalized macromolecular photoswitch and its synthetic method |
| WO2023072242A1 (en) * | 2021-10-28 | 2023-05-04 | 中国石油化工股份有限公司 | Composition for preparing polycaprolactone shape memory material, and polycaprolactone shape memory material, preparation method therefor, and application thereof |
| CN116478063A (en) * | 2023-04-19 | 2023-07-25 | 中国科学院兰州化学物理研究所 | Azobenzene monomer, high strength and low friction coefficient shape memory polymer material with photoresponsive properties, preparation method and application |
| CN117304450A (en) * | 2023-11-24 | 2023-12-29 | 西南石油大学 | Blending type light response benzoxazine material and preparation method thereof |
| CN117304450B (en) * | 2023-11-24 | 2024-02-13 | 西南石油大学 | Blending type light response benzoxazine material and preparation method thereof |
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