CN101747486B - Light-induced shape-memory polymer and preparation method thereof - Google Patents

Light-induced shape-memory polymer and preparation method thereof Download PDF

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CN101747486B
CN101747486B CN 200910156931 CN200910156931A CN101747486B CN 101747486 B CN101747486 B CN 101747486B CN 200910156931 CN200910156931 CN 200910156931 CN 200910156931 A CN200910156931 A CN 200910156931A CN 101747486 B CN101747486 B CN 101747486B
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diisocyanate
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transition temperature
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CN101747486A (en )
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吴林波
靳春丽
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浙江大学
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Abstract

The invention discloses a light-induced shape-memory polymer and a preparation method thereof. The light-induced shape-memory polymer is a thermoplastic polyurethane multi-block copolymer having N-substituted cinnamamide photosensitive structure units, wherein the main transformation temperature of a soft block is no more than 50 DEG C. The light-induced shape-memory polymer is prepared by reactions of an N-dihydroxyalkyl cinnamamide photosensitive monomer, an alpha,omega-hydroxyl-terminated polymer, a low-molecular weight chain extender and diisocyanate. The light-induced shape-memory polymer has easily-adjustable structural behaviors, can be degradable or nondegradable, has high processability, can obtain a temporary shape under the action of an external force and the irradiation of ultraviolet light with a wavelength greater than 260 nanometers, and can restore original shape under the irradiation of ultraviolet light with a wavelength smaller than 260 nanometers. Without temperature dependency, the light-induced shape-memory effectexcitation of the light-induced shape-memory polymer can be performed at room temperature and also can be performed at a long distance by means of optical fibers and the like. The preparation method is simple, feasible, universal and favorable for the realization of commercialization.

Description

一种光致形状记忆聚合物及其制备方法 An optical shape memory polymers and their method of preparation

技术领域 FIELD

[0001] 本发明涉及功能性高分子材料及其制备方法,尤其涉及一种光致形状记忆聚合物及其制备方法。 [0001] The present invention relates to functional high polymer material and its preparation method, in particular, relates to an optical shape memory polymers and their method of preparation.

背景技术 Background technique

[0002] 形状记忆聚合物是一类功能性或智能聚合物,当其由一次成型获得的起始形状被二次加工成临时形状后,它能“记忆”起始形状,并在外界刺激作用下恢复起始形状。 [0002] Shape memory polymers are a class of functional polymers or smart, when the initial shape which is obtained by forming a temporary shape into a secondary processing, it "remembers" starting shape, and the outside stimulation restore the original shape. 利用其形状记忆功能,形状记忆聚合物可广泛用于结构连接件、包装材料、印刷材料、纺织品等。 Using its shape memory, shape memory polymer can be used in structural connector, packaging materials, printing materials, textiles and the like. 形状记忆聚合物中,可生物降解形状记忆聚合物由于同时具有降解吸收性和形状记忆功能, 还可以用作医用植入材料和药物控制释放的载体,如医用缝合线、防止管道再狭窄植入支架、血管接合/绑扎、肌腱固定、骨固定等。 A shape memory polymer, a shape memory biodegradable polymer degradation due to simultaneous absorption and having a shape memory function can also be used as medical implant materials and drug carriers controlled release, medical sutures, implants prevent restenosis conduit stents, vascular engaging / banding, fixed tendon, bone fixation and the like. 与形状记忆合金(SMA)相比,可生物降解形状记忆聚合物具有以下优越性:(1)应变量大,可达100%以上,而SMA仅8% ; (2)可生物降解, 术后不用取出,患者可免除二次手术的痛苦;C3)可接受核磁共振检查;(4)对毗邻组织的压迫损伤较轻;(¾加工方便,可以制成小尺寸的临时形状,特别适合微创手术。 Compared with a shape memory alloy (SMA), shape memory biodegradable polymer has the following advantages: (1) large strain up to 100%, while only 8% SMA; (2) a biodegradable, after without removing the patient from pain can be a secondary operation; a C3) pharmaceutically MRI; (4) damage to adjacent tissue compression less; (¾ easy processing, the temporary shape can be made small size, especially for minimally invasive surgery.

[0003] 形状记忆聚合物中,触发形状记忆效应的外界刺激手段有多种,如热、光、电、磁等,甚至吸收水分也可用于触发形状记忆效应。 [0003] The shape memory polymer, the external stimulus to trigger a variety of shape memory effect, such as heat, light, electricity, magnetism, and even moisture absorption can also be used to trigger the shape memory effect. 其中,热触发(或称热致形状记忆)是目前研究开发的重点,如US6160084、US20040015187、US20060140999、US6281262, US6281262, W09942147、CN1852931、CN03114594. 9、CN1693362、CN1563132、CN1569261、CN1544096、 CN1887364、CN1820793、CN1911983、CN1563132、CN1693362、CN1693362、Polymersfor Advanced Technologies (16 :608-615,2005), Science (296 :1673-6,2002)等报道。 Wherein the thermal trigger (also known as thermally induced shape-memory) is the research and development priorities, such as US6160084, US20040015187, US20060140999, US6281262, US6281262, W09942147, CN1852931, CN03114594. 9, CN1693362, CN1563132, CN1569261, CN1544096, CN1887364, CN1820793, CN1911983, CN1563132, CN1693362, CN1693362, Polymersfor Advanced Technologies (16: 608-615,2005), Science (296: 1673-6,2002) reported. 2005 年,《Nature》034卷14期,P879_88》杂志报道了两种不可生物降解的光致形状记忆聚合物。 In 2005, "Nature" 034 Volume 14, P879_88 "magazine reported nonbiodegradable two photo-shape memory polymer. 它们分别是通过自由基共聚法制备的含光敏基团的自由基交联共聚物和通过互穿网络法制备的含星形光敏化合物的互穿网络聚合物。 They are radical cross-linked copolymer prepared by free-radical copolymerization of a photosensitive group-containing polymer and interpenetrating network comprising a star photosensitive compound prepared by an interpenetrating network of law. 经加工成型的器件在室温下经外力作用而变形,经波长大于260纳米的紫外光照射后,将形变部分固定住,经另一波长小于260纳米的紫外光照射,形状恢复。 Processed molding device deformed by an external force at room temperature, after UV irradiation at wavelengths greater than 260 nm, the deformation portion fixed by ultraviolet light of another wavelength less than 260 nm, the shape recovery.

[0004] 与热致形状记忆效应相比,光致形状记忆效应可在较宽的温度范围内利用紫外光激发,没有强的温度依赖性,并可利用光纤等手段非体表部位实现远程激发。 [0004] Compared with thermally induced shape memory effect, light-induced shape memory effect can be excited with ultraviolet light in a wide temperature range, no strong temperature dependence, and the like with a non-fiber portion of the body surface remote excitation means . 这些特点对某些应用非常有利,例如在医学临床应用时能避免高温加热带来的不适,远程激发特别利于微创介入治疗。 These characteristics are very advantageous for certain applications, such as in medical clinical application to avoid the discomfort caused by high-temperature heating, remote inspire especially conducive to minimally invasive treatment. 因此,不仅要研究开发不可降解的光致形状记忆聚合物,也有必要合成可生物降解吸收的光致形状记忆聚合物。 Accordingly, not only to the research and development of light-induced non-degradable shape memory polymer, it is necessary photocurable synthetic biodegradable shape memory polymer is absorbed. 与可生物降解热致形状记忆聚合物和不可生物降解的光致形状记忆聚合物相比,制备可生物降解光致形状记忆聚合物要困难得多,还基本停留在概念设计上。 And the biodegradable shape memory polymer and a thermally non-biodegradable shape memory polymer compared with the light, the light of making a biodegradable shape memory polymer is much more difficult, and substantially remain in the conceptual design.

[0005] 因此,研究开发新型光致形状记忆聚合物及其制备方法,尤其是可生物降解光致形状记忆聚合物及其制备方法,尤其是能同时用于制备不可降解和可生物降解的光致形状记忆聚合物的方法,还是有待解决的技术的问题。 [0005] Accordingly, research and development of new optical shape memory polymers and their method of preparation, in particular a photo-biodegradable polymers and their method of preparation, especially the preparation of light can be used for both non-biodegradable and biodegradable the method of shape memory polymers, or technical problems to be solved. 发明内容 SUMMARY

[0006] 本发明的目的是克服现有技术的不足,提供一种光致形状记忆聚合物及其制备方法。 [0006] The object of the present invention is to overcome the disadvantages of the prior art, providing a shape memory polymer and a method for preparing photo.

[0007] 光致形状记忆聚合物是含有如下la、lb或Ic所示的N-取代肉桂酰胺光敏结构单元的热塑性聚氨酯类多嵌段共聚物,其软段的主转变温度不高于50°C ;它由(l)0.5Wt%〜 [0007] The shape memory polymer is a light containing the following la, N- shown lb Ic or substituted cinnamic amide thermoplastic polyurethane based photosensitive multiblock copolymer of the structural unit, which main soft segment transition temperature not higher than 50 ° C; it is a (l) 0.5Wt% ~

二羟烷基肉桂酰胺、(2)90wt%〜 20wt%的主转变温度不高于50°C的α, ω -端羟基聚合物A、(3) 0〜5wt%的小分子扩链剂、(4) 0〜75wt%的玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的α,ω-端羟基 Dihydroxy cinnamic acid amide group, (2) 90wt% ~ 20wt% of the main transition temperature of the α 50 ° C, ω - terminal hydroxyl polymer A, (3) 0~5wt% small molecule chain extender, (4) 0~75wt% of the glass transition temperature or melting point of not lower than 50 ° C and the ratio of [alpha], [omega] the main transition temperature of the polymer terminal hydroxyl group of a is at least of α 20 ° C, ω- terminal hydroxyl group

聚合物B和(5) [0008] And polymer B (5) [0008]

:异氰酸酯反应而制得; : Isocyanate-reactive prepared;

I I

1c 1c

1a 1b 。 1a 1b.

[0009] 一种光致形状记忆聚合物的制备方法,其特征在于如下步骤: [0009] A method for producing photoinduced shape memory polymer, characterized by the steps of:

[0010] 1)将0. 5wt%〜 二羟烷基肉桂酰胺、90wt%〜 20wt%的主转变温度不高于50°C的α,ω-端羟基聚合物A和二异氰酸酯在0〜的催化剂存在下在50-180°C下反应,异氰酸酯基与步骤1)和2)中所有反应物的羟基和氨基之和的摩尔比为1〜1.2 : 1,制得预聚物; [0010] 1) 0. 5wt% ~ dihydroxy cinnamic amide group, 90wt% ~ 20wt% of the main transition temperature of the α 50 ° C, ω- terminal hydroxyl polymer A and a diisocyanate in the 0~ presence of a catalyst at 50-180 ° C 1~1.2 1) molar ratio of isocyanate groups in step 2) and the hydroxyl and amino groups and all reactants are: 1, to obtain a prepolymer;

[0011 ] 2)将预聚物与0. 5〜5wt %的小分子扩链剂或5〜75wt %的玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的α,ω-端羟基聚合物B在50-180°C下反应,制得光致形状记忆聚合物。 [0011] 2) The prepolymer 0. 5~5wt% small molecule chain extender, or 5~75wt% of the glass transition temperature or melting point of not lower than 50 ° C and the ratio of the α, ω- terminal hydroxyl group α transition temperature of the main polymer a is at least at 20 ° C, [omega] B terminal hydroxyl polymer reaction at 50-180 ° C, to obtain a photo-shape memory polymer.

[0012] 另一种光致形状记忆聚合物的制备方法包括如下步骤: [0012] Another method of preparing a photo-shape memory polymer comprises the steps of:

[0013] 1)将0. 5wt%〜25衬%的N-二羟烷基肉桂酰胺、90wt%〜 20wt%的主转变温度不高于50°C的α,ω-端羟基聚合物Α、5〜75wt%的玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的α,ω-端羟基聚合物B和二异氰酸酯在0〜的催化剂存在下在50〜180°C下反应,异氰酸酯基与步骤1)和2)中所有反应物的羟基和氨基之和的摩尔比为1〜1. 2 : 1,制得预聚物; [0013] 1) The lining 0. 5wt% ~25% of cinnamic acid amide N- dihydroxyalkyl, 90wt% ~ 20wt% of the main transition temperature of the α 50 ° C, ω- terminal hydroxyl polymer Α, 5~75wt% of the glass transition temperature or melting point of not lower than 50 ° C and the ratio of [alpha], [omega] the main transition temperature of the polymer terminal hydroxyl group of a is at least of α 20 ° C, ω- polymer terminal hydroxyl group and B diisocyanate in the presence of a catalyst 0~ at 50~180 ° C 1) molar ratio of isocyanate groups in step 2) and the hydroxyl and amino groups of all reactants and 1~1 is 2: 1, system prepolymers;

[0014] 2)将预聚物与0. 5〜5wt%的小分子扩链剂在50_180°C下反应,制得所述的光致形状记忆聚合物。 [0014] 2) The prepolymer 0. 5~5wt% small molecule chain extender at 50_180 ° C, photo-shape memory polymer prepared according to.

[0015] 另一种光致形状记忆聚合物的制备方法是:将0. 5wt%〜25wt%的N-二羟烷基肉桂酰胺、90wt%〜20wt%的主转变温度不高于50°C的α,ω -端羟基聚合物A和二异氰酸酯直接在0〜的催化剂存在下在50-180°C下反应,异氰酸酯基与总的羟基的摩尔比为1〜1.2 : 1,制得所述的光致形状记忆聚合物。 [0015] Another method of preparing a photo-shape memory polymer is: A 0. 5wt% ~25wt% of cinnamic acid amide N- dihydroxyalkyl, 90wt% ~20wt% of the main transition temperature of not above 50 ° C the α, ω - a molar ratio of the polymer terminal hydroxyl groups and a diisocyanate in the presence of a catalyst 0~ directly at 50-180 ° C the reaction, the isocyanate groups to total hydroxyl is 1~1.2: 1, to obtain the photoinduced shape memory polymer.

[0016] 所述的N- 二羟烷基肉桂酰胺为N,N- 二羟乙基肉桂酰胺、N,N- 二羟异丙基肉桂酰胺或N-[2-羟基-1-(羟甲基)乙基]-肉桂酰胺;所述的小分子扩链剂为乙二醇、1,4- 丁 [0016] an N- dihydroxyalkyl cinnamic amide is N, N- dihydroxyethyl cinnamic amide, N, N- isopropyl-dihydroxy cinnamic acid amide or N- [2- hydroxy-1- (hydroxymethyl yl) ethyl] - cinnamic amide; a small molecule chain extender is ethylene glycol, 1,4-

6二醇、2,3_ 丁二醇、二甘醇、1,6_己二醇、环己二醇、环己烷二甲醇、苯二胺、联苯二胺、3, 3' - 二甲基_4,4' -联苯二胺、3,3' - 二氯_4,4' -联苯二胺、4,4' - 二氨基二苯甲烷、3, 3' - 二甲氧基_4,4' - 二氨基二苯甲烷或3,3' - 二氯_4,4' - 二氨基二苯甲烷;所述的二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、2,2,4_三甲基己烷二异氰酸酯、2,4,4_三甲基己烷二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、甲基环己基二异氰酸酯、二环己基甲烷二异氰酸酯或四甲基苯二亚甲基二异氰酸酯;所述的催化剂为辛酸亚锡、二月桂酸二丁基锡。 6-diol, 2,3_-butanediol, diethylene glycol, 1,6_ hexanediol, cyclohexanediol, cyclohexanedimethanol, p-phenylenediamine, benzidine, 3, 3 '- dimethyl yl _4,4 '- benzidine, 3,3' - dichloro _4,4 '- benzidine, 4,4' - diaminodiphenylmethane, 3, 3 '- dimethoxy _4,4 '- diaminodiphenyl methane, or 3,3' - dichloro _4,4 '- diaminodiphenylmethane; said diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene methyl diisocyanate, 2,2,4_ trimethyl hexane diisocyanate, 2,4,4_ trimethyl hexane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene - 1,5-diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate or tetramethylxylylene diisocyanate, dimethylene diisocyanate; the catalyst is stannous octoate, dibutyl tin dilaurate.

[0017] 所述的α,ω-端羟基聚合物A为主转变温度不高于50°C的且含α,ω-端羟基的聚酯、聚醚、聚硅氧烷、聚碳酸酯、聚酯酰胺、聚醚酯、聚酯碳酸酯或聚烯烃;所述的α, ω-端羟基聚合物B为玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A 的主转变温度至少高20°C的且含α,ω-端羟基的聚酯、聚碳酸酯、聚酯酰胺或聚烯烃。 And containing α, ω- terminal hydroxyl polyester α [0017] according to, [omega] A polymer terminal hydroxyl group is not the main transition temperature of above 50 ° C, polyether, polysiloxane, polycarbonate, polyester amides, polyether esters, polyester carbonate or polyolefin; the α, ω- terminal hydroxyl polymer B glass transition temperature or melting point of not lower than 50 ° C and the ratio of the α, ω- end a transition temperature of the primary hydroxyl group of the polymer is at least at 20 ° C and containing α, ω- terminal hydroxyl polyesters, polycarbonates, polyester amides, or polyolefin.

[0018] 所述的α,ω-端羟基聚合物A为主转变温度不高于50°C的且含α,ω-端羟基的聚己内酯、聚(三亚甲基碳酸酯)、聚丁二酸己二醇酯、聚丁二酸丁二醇酯、聚丁二酸丙二醇酯、聚丁二酸乙二醇酯、聚丁二酸一缩二乙二醇酯、聚己二酸己二醇酯、聚己二酸丁二醇酯、 聚己二酸丙二醇酯、聚己二酸乙二醇酯、聚己二酸一缩二乙二醇酯或它们的共聚物;或者为主转变温度不高于50°C的且含α,ω-端羟基的聚乙二醇、聚丙二醇、聚四氢呋喃和它们的共聚物;或者为主转变温度不高于50°C的且含α,ω-端羟基的聚丁二烯、聚异戊二烯或丁二烯-丙烯腈共聚物。 [0018] the α, ω- A terminal hydroxyl polymer-based transition temperature of not above 50 ° C and containing α, ω- terminal hydroxy polycaprolactone, poly (trimethylene carbonate), poly hexyl glycol succinate, polybutylene succinate, polybutylene succinate, propylene glycol, polyethylene succinate, polyethylene succinate, diethylene glycol, polyethylene adipate glycol esters, polyethylene adipate, polypropylene adipate, polyethylene adipate, polypropylene adipate, diethylene glycol or a copolymer thereof; or main transition temperature not above 50 ° C and containing α, ω- terminal hydroxyl group of polyethylene glycol, polypropylene glycol, polytetrahydrofuran and copolymers thereof; or the main transition temperature of not above 50 ° C and containing α, ω - terminal hydroxyl polybutadiene, polyisoprene or polybutadiene - acrylonitrile copolymers.

[0019] 所述的α,ω-端羟基聚合物B为玻璃化温度或熔点不低于50°C且比所述的α, ω-端羟基聚合物A的主转变温度至少高20°C的且含α,ω-端羟基的聚乳酸、聚羟基乙酸、聚对二氧环己酮、聚丁二酸丁二醇酯、聚丁二酸乙二醇酯、聚己二酸丁二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸环己烷二甲醇酯或它们的共聚物。 α [0019] according to, ω- terminal hydroxyl polymer B glass transition temperature or melting point of not lower than 50 ° C and the ratio of [alpha], [omega] end of the main transition temperature of the hydroxyl polymer A is at least 20 ° C and containing α, ω- terminal hydroxyl group of polylactic acid, polyglycolic acid, poly dioxanone, polybutylene succinate, polyethylene succinate, polybutylene adipate esters, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, cyclohexane dimethanol esters or copolymers thereof.

[0020] 本发明提供的光致形状记忆聚合物为含有N-取代肉桂酰胺光敏结构单元的热塑性氨酯类多嵌段共聚物,具有良好的成型加工性,并可在较宽的温度范围内利用紫外光激发,没有强的温度依赖性;可利用光纤等手段非体表部位实现远程激发。 [0020] The photo-shape memory polymer provided for the present invention comprises a thermoplastic urethane-based multi-block copolymers of the photosensitive N- substituted cinnamic amide structural unit, has excellent moldability, and can range within wide temperature excitation with ultraviolet light, there is no strong temperature dependence; available non-fiber portion of the body surface means of remote excitation.

[0021] 本发明提供的光致形状记忆聚合物既可是不可降解的光致形状记忆聚合物,也可是生物降解的光致形状记忆聚合物,可通过改变多嵌段共聚物中的链段结构来调节其生物降解性和其它性能,以满足在使用时对力学性能和降解速率的要求。 [0021] The photo-shape memory polymer provided by the present invention may be either non-degradable shape memory polymer light, the light may also be biodegradable shape memory polymer, a segment multiblock copolymer structure by changing the to adjust its biodegradability and other properties to meet the requirements on the mechanical properties and degradation rates in use.

[0022] 本发明提供的可生物降解光致形状记忆聚合物,在临床应用时能够避免热致形状记忆时对体温的敏感性而带来的不便及高温加热带来的不适;也可利用可实现远程激发的特点在体内实现形状恢复,方便用于微创介入治疗。 [0022] The present invention provides a photo-biodegradable shape memory polymers, in clinical applications to avoid the inconvenience and high temperature thermal shape memory body temperature sensitivity brought heating of discomfort; may also be utilized remote excitation characteristics to achieve recovery in the body shape, convenient for the minimally invasive treatment.

[0023] 本发明提供的光致形状记忆聚合物的制备方法简单可行,具有通用性,既可用于可生物降解光致形状记忆聚合物的制备,也可用于不可降解的光致形状记忆聚合物的制备,有利于实现商品化。 [0023] The method of preparing a photo-shape memory polymer of the present invention provides a simple and practical, versatile, both for the preparation of shape memory polymer light biodegradable, also be used for light-induced non-degradable shape memory polymer preparation will help to achieve commercialization.

附图说明 BRIEF DESCRIPTION

[0024] 图1是光致形状记忆聚合物1的红外光谱。 [0024] FIG. 1 is a shape memory polymer light IR 1. 1727(^^1757(3!^1处为聚己内酯和聚乳酸中的酯基吸收峰,1603CHT1和1649cm—1为光敏结构单元中苯环和CH = CH双键的吸收;[0025] 图2是光致形状记忆聚合物1的1H NMR核磁谱。6. 8-7. 6ppm为肉桂酰基中的苯环和CH = CH双键的化学位移;1-1. 5ppm和5. Oppm为聚合物链段中CH3和CH的化学位移; 其它为聚己内酯和连接单元中氢原子的化学位移。 ! 1727 (1757 ^^ (^ 3 at a polycaprolactone and polylactic acid ester group absorption peak, 1603CHT1 1649cm-1, and a photosensitive benzene ring and the structural unit CH = CH double bond absorption; [0025] FIG 2 is a shape memory polymer light 1H NMR Nmr .6 8-7 6ppm as cinnamoyl group and the benzene ring in the chemical shifts of CH = CH double bond 1;... 1-1 5ppm and 5. Oppm of chemical shifts of the polymer segment CH3 and CH; other chemical shift of polycaprolactone and a connection unit of a hydrogen atom.

具体实施方式 detailed description

[0026] 本发明提供的光致形状记忆聚合物为含有N-取代肉桂酰胺光敏结构单元、软段和硬段的热塑性聚氨酯类多嵌段聚合物。 Photo shape memory polymer provided herein [0026] The present N- substituted cinnamic amide containing structural units photosensitive, thermoplastic polyurethane-based soft and hard segments of the multi-block polymer. 其软段为聚合物A链段(以下简称A链段),软段的主转变温度(主转变温度为无定形聚合物的玻璃化温度或结晶性聚合物的熔融温度)不高于50°C ;硬段为二氨酯或二脲结构单元,或者由二氨酯或二脲结构单元与小分子扩链剂残基共同构成硬段,或者由二氨酯或二脲结构单元与聚合物B链段(以下简称B链段)共同构成硬段,硬段的玻璃化温度或熔点不低于50°C且比软段的主转变温度至少高20°C,硬段能形成物理交联结构。 A soft segment which is a segment of polymer (hereinafter referred to as segment A), a main soft segment transition temperature (glass transition temperature of the main temperature of amorphous polymers or the melting temperature of the crystalline polymer) is not higher than 50 ° C; hard segment is two diurea or urethane structural units, or by two urethane or urea structural units of two small molecule chain extender constituting the hard segment residues together, or by two or urethane structural units and diurea polymer B segment (hereinafter referred to as segment B) together constituting the hard segment, a melting point or glass transition temperature of the hard segment is not lower than 50 ° C and the temperature of at least 20 ° C higher than the primary transition of the soft segment, the hard segments can form physical crosslinking structure.

[0027] 本发明中,当只有A链段而没有B链段且A链段为可生物降解链段,或者同时含有A链段和B链段且它们均为可生物降解链段时,本发明提供的光致形状记忆聚合物为可生物降解形状记忆聚合物;当只有A链段而没有B链段且A链段为不可生物降解链段,或者同时含有A链段和B链段且它们均为不可生物降解链段时,本发明提供的光致形状记忆聚合物为不可生物降解的形状记忆聚合物;当同时含有A链段和B链段且它们之中有且只有一种为可生物降解链段时,本发明提供的光致形状记忆聚合物为部分生物降解的形状记忆聚合物。 [0027] In the present invention, when not only the A segment and B segment is a segment A and a biodegradable segment or segments containing the A and B segments and they are simultaneously when the biodegradable segment, the present the invention provides a shape memory polymer photo degradation of the shape memory polymer is biodegradable; when only segment a and segment B and not a segment is non-biodegradable segment or segments containing both a and B segments and when they are non-biodegradable segment, the present invention provides a photoinduced shape memory polymer is non-biodegradable shape memory polymer; contain both when a and B segments and segments and only one of them there is when the biodegradable segment, a photo-shape memory polymer of the present invention is to provide a partially biodegradable shape memory polymers.

[0028] 在外力作用下,该聚合物发生变形,同时以波长大于260纳米的紫外光照射,光敏结构单元发生环加成反应,生成额外的光致交联结构,使该聚合物能保持或部分保持变形后的临时形状;使用时在另一波长小于260纳米的紫外光照射下,光致交联结构解开,恢复其起始形状。 [0028] Under an external force, the deformed polymer, while irradiated with ultraviolet light at wavelengths greater than 260 nm, the photosensitive structural unit cycloaddition reaction to generate additional photo-crosslinked structure, or the polymer can be maintained temporary holding part deformed shape; UV irradiation at further wavelengths less than 260 nanometers, photo-crosslinked structure untied when used, to recover its original shape.

[0029] 本发明中,光致形状记忆聚合物采用N- 二羟烷基肉桂酰胺光敏单体、α,ω-端羟基聚合物、小分子扩链剂等与二异氰酸酯反应制得,制备方法与传统的聚氨酯制备方法类似,简单可行。 [0029] In the present invention, a shape memory polymer using a photo-N- dihydroxyalkyl cinnamide photosensitive monomer, α, ω- terminal hydroxyl polymer, a small molecule chain extender with a diisocyanate or the like prepared by the reaction, preparing and similar polyurethanes prepared by conventional methods, simple and feasible. 光敏单体、α,ω-端羟基聚合物A和B、小分子扩链剂均为含活泼氢(羟基或氨基)的反应物,其用量为基于所有活泼氢反应物的总质量(即光敏单体、α,ω-端羟基聚合物A和B、小分子扩链剂之和)的百分数。 Photosensitive monomer, α, ω- terminal hydroxyl polymers A and B, are small molecule chain extender containing active hydrogen (a hydroxyl group or an amino group) of the reaction product in an amount based on the total mass of all active hydrogen reactant (i.e., photosensitive monomeric α, ω- terminal hydroxyl polymers a and B, a small molecule chain extender and) the percentage. 制备时可不加催化剂,也可加入聚氨酯合成的常用催化剂。 Not to add the catalyst preparation, the catalyst may also be added conventional polyurethane synthesis. 当制备可生物降解光致形状记忆聚合物时,可采用通过FDA认证的辛酸亚锡作为催化剂,以保证产品良好的生物相容性。 When preparing the biodegradable shape memory polymer is light, it can be certified by the FDA stannous octoate as a catalyst, the product to ensure good biocompatibility. 催化剂用量为所有含活泼氢反应物总质量的0〜lwt%。 Amount of catalyst 0~lwt% of the total mass of all active hydrogen-containing reactants. 二异氰酸酯的用量如下控制:异氰酸酯基与所有反应物的羟基和氨基之和的摩尔比为1〜1. 2 : 1。 The amount of diisocyanate following controls: the molar ratio of hydroxy and amino groups with the isocyanate and all of the reactants are 2 1~1: 1.

[0030] 本发明中,采用加装了紫外灯的电子材料试验机,通过光致机械循环实验测定光致形状记忆效应。 [0030] The present invention employs a UV lamp installed electronic materials testing machine, by photo-photo-mechanical shape memory effect cycle test was measured. 将试样以lOmm/min的速度拉伸到应变ε m ;在保持应变不变的情况下,将试样在一定光强的波长为的紫外光照射一定时间,撤除外力,用游标卡尺测量无应力条件下的应变%,按ε u/ε m计算应变固定率&;然后,将该试样在一定光强的波长为的紫外光照射一定时间,测量残留应变%,按Rr= (^-^丨/^计算应变恢复率艮。 The sample rate at lOmm / min to a tensile strain ε m; strain remains constant in the case of a sample in a certain light intensity of ultraviolet light having a wavelength of a predetermined time, the removal of the external force, measured with a caliper unstressed % strain condition, press ε u / ε m & calculate the strain rate is fixed; then, the sample was a certain light intensity of ultraviolet light having a wavelength of a predetermined time, the measurement of residual strain% by Rr = (^ - ^ Shu / ^ Gen calculate the strain recovery rate.

[0031] 下面通过实施例进一步描述本发明的实施方式,但本发明的范围不限于这些实施例。 [0031] By following examples further describe embodiments of the present invention, but the scope of the present invention is not limited to these embodiments. [0032] 实施例1 [0032] Example 1

[0033] 1)在烧瓶中加入α,ω -端羟基液体聚己内酯(分子量为530,3. 1克)、N,N- 二羟乙基肉桂酰胺O. 5克)和1,4_ 二氧六环M克,放入油浴中,搅拌下加热至80°C,并通氮处理0. 5小时;再加入0. 2wt %的辛酸亚锡及六亚甲基二异氰酸酯,异氰酸酯基与步骤1) 和2)中所有反应物的总羟基的摩尔比为1. 1 : 1,在氮气保护和80〜85°C下反应3小时, 制得预聚物溶液。 [0033] 1) In a flask was added α, ω -. Terminal hydroxyl liquid polycaprolactone (molecular weight 530,3 1 g), N, N- dihydroxyethyl cinnamide O. 5 g) and 1,4_ M g of dioxane, placed in an oil bath and heated with stirring to 80 ° C, and nitrogen-treated 0.5 hours; then added 0. 2wt% of stannous octoate and hexamethylene diisocyanate, the isocyanate groups and) the molar ratio of the total hydroxyl groups) and 2 step 1 of all reactants is 1.1: 1, the reaction for 3 hours under nitrogen and 80~85 ° C, to obtain a prepolymer solution.

[0034] 2)在预聚物溶液中加入α,ω -端羟基聚L-乳酸(熔点170°C,4. 4克)、1,4_ 二氧六环55. 6克,在氮气保护和80〜85°C下反应6小时;将反应产物溶液倒入玻璃皿中成膜,待溶剂自然挥发后真空干燥,得到光致形状记忆聚合物膜1。 [0034] 2) added to the prepolymer solution α, ω -. Terminal hydroxyl groups of poly L- lactic acid (m.p. 170 ° C, 4 4 g), 1,4_ dioxane 55.6 g, in nitrogen atmosphere and the reaction at 80~85 ° C 6 hours; the reaction product solution was poured into a glass dish deposition, and dried in vacuo until natural volatile solvent, to obtain a photo-film shape memory polymer.

[0035] 实施例2 [0035] Example 2

[0036] 1)在烧瓶中加入α,ω-端羟基液体聚己内酯(分子量为530,1. 5克)和Ν,Ν_ 二羟乙基肉桂酰胺(1. 0克),放入油浴中,搅拌下加热至50°C,并通氮处理0. 5小时;再加入六亚甲基二异氰酸酯和1,4_ 二氧六环M克,异氰酸酯基与步骤1)和幻中所有反应物的总羟基的摩尔比为1.1 : 1,在氮气保护和50°C下反应8小时,制得预聚物溶液; [0036] 1) A flask was charged α, ω- terminal hydroxyl liquid polycaprolactone (molecular weight of 530,1. 5 g) and Ν, Ν_ dihydroxyethyl cinnamic amide (1.0 g), into the oil bath was heated to 50 ° C, and nitrogen-treated 0.5 hours; then hexamethylene diisocyanate and 1,4_ dioxane M g isocyanate groups in step 1), and all reactions magic molar ratio of the total hydroxyl groups was 1.1: 1, reacted for 8 hours under nitrogen and 50 ° C, to prepare the prepolymer solution;

[0037] 2)在预聚物溶液中加入α,ω-端羟基聚L-乳酸(熔点170°C,7.5克),在氮气保护和80〜85°C下反应6小时;将反应产物溶液倒入玻璃皿中成膜,待溶剂自然挥发后真空干燥,得到光致形状记忆聚合物膜2。 [0037] 2) added to the prepolymer solution α, the terminal hydroxyl groups of poly [omega] L- lactic acid (m.p. 170 ° C, 7.5 g) under nitrogen and the reaction 80~85 ° C 6 hours; the reaction product solution poured into a glass dish forming, after the solvents volatilize naturally dried in vacuo to give the photo film 2 is a shape memory polymer.

[0038] 实施例3 [0038] Example 3

[0039] 1)在烧瓶中加入α,ω-端羟基聚己内酯-乙交酯共聚物(分子量为2000,熔点约25°C )8克和N-[2-羟基-1-(羟甲基)乙基]-肉桂酰胺1. 5克,放入油浴中,搅拌下加热至80°C,并通氮处理0. 5小时;再加入辛酸亚锡的甲苯溶液(含辛酸亚锡0. 04克、甲苯4克)、甲苯M克和甲苯二异氰酸酯,异氰酸酯基与步骤1)和2)中所有反应物的总羟基的摩尔比为1 : 1,在氮气保护和80〜85°C下反应3小时,制得预聚物溶液。 [0039] 1) In a flask was added α, [omega] terminal hydroxyl polycaprolactone - glycolide copolymer (molecular weight of 2000, a melting point of about 25 ° C) 8 g of and N- [2- hydroxy-1- (hydroxymethyl methyl) ethyl] - cinnamides 1.5 g, placed in an oil bath and heated with stirring to 80 ° C, and nitrogen-treated 0.5 hours; stannous octoate was added a toluene solution (stannous octoate 0.04 g, toluene 4 g), 1) the molar ratio of toluene M g and toluene diisocyanate, the isocyanate groups of step total hydroxyl 2) and all reactants is 1: 1, in a nitrogen atmosphere and 80~85 ° for 3 hours under C, to obtain a prepolymer solution.

[0040] 2)在预聚物溶液中加入1,4_ 丁二醇0. 5克,在氮气保护和80〜85°C下反应6小时;将反应产物溶液倒入玻璃皿中成膜,待溶剂自然挥发后真空干燥,得到光致形状记忆聚合物膜3。 [0040] 2) added to the prepolymer solution, 0.5 g 1,4_-butanediol, nitrogen and reacted at 80~85 ° C 6 hours; the reaction product solution was poured into a glass dish deposition, to be after volatile solvent was naturally dried in vacuo to give a photo-shape memory polymer film 3.

[0041] 实施例4 [0041] Example 4

[0042] 在烧瓶中加入α,ω-端羟基聚己二酸乙二醇丙二醇共聚酯(室温下为蜡状固体, 熔点不超过50°C)9克和Ν,Ν-二羟乙基肉桂酰胺1克,放入油浴中,搅拌下加热至80°C,并通氮处理0.5小时;再加入甲苯M克及二苯基甲烷二异氰酸酯,异氰酸酯基与步骤1)和2) 中所有反应物的总羟基的摩尔比为1. 1 : 1,在氮气保护和80〜85°C下反应8小时;将反应产物溶液倒入玻璃皿中成膜,待溶剂自然挥发后真空干燥,得到光致形状记忆聚合物膜4。 [0042] In a flask was added α, [omega] terminal hydroxyl polyethylene adipate glycol copolyester (at room temperature a waxy solid, melting point not exceeding 50 ° C) 9 g of and Ν, Ν- dihydroxyethyl cinnamamide 1 g, placed in an oil bath with stirring and heated to 80 ° C, and a nitrogen for 0.5 hours; then toluene was added M g and diphenylmethane diisocyanate, the isocyanate groups in step 1) and 2) all the molar ratio of total hydroxyl reactants is 1.1: 1, and reacted under nitrogen 80~85 ° C 8 hours; the reaction product solution was poured into a glass dish deposition, and dried in vacuo until natural volatile solvent, to give photo film 4 is a shape memory polymer.

[0043] 实施例5 [0043] Example 5

[0044] 1)在烧瓶中加入α,ω -端羟基液态聚二甲基硅氧烷2克和N,N- 二羟乙基肉桂酰胺0. 05克,放入油浴中,搅拌下加热至180°C,并通氮处理0.5小时;冷却至100°C,再加入甲苯二异氰酸酯,异氰酸酯基与所有反应物的总羟基的摩尔比为1.1 : 1,在氮气保护和50°C下反应3小时,制得预聚物。 [0044] 1) In a flask was added α, ω - terminal hydroxyl liquid polydimethylsiloxane 2 g and N, N- dihydroxyethyl cinnamic amide 0.05 g, placed in an oil bath and heated with stirring to 180 ° C, and a nitrogen for 0.5 hours; cooled to 100 ° C, and then added tolylene diisocyanate, the molar ratio of the total hydroxyl isocyanate groups with all of the reactants is 1.1: 1, the reaction under a nitrogen atmosphere and 50 ° C for 3 hours to prepare a prepolymer.

[0045] 2)在预聚物中加入α,ω-端羟基聚对苯二甲酸丁二醇酯(分子量约2000,熔点约160°C )7. 95克,在氮气保护和180°C下反应3小时,得到光致形状记忆聚合物5。 [0045] 2) in the prepolymer was added α, [omega] terminal hydroxyl poly (butylene terephthalate) (molecular weight of about 2000, a melting point of about 160 ° C) 7. 95 g, under nitrogen and 180 ° C for 3 hours, to obtain a photo-5 shape memory polymer. [0046] 聚合物5经热压,得到片材。 [0046] Polymer 5 was hot-pressed to obtain a sheet.

[0047] 实施例6 [0047] Example 6

[0048] 1)在烧瓶中加入α,ω-端羟基液体聚丁二烯(分子量为2000,常温下为液体)3 克和N,N- 二羟乙基肉桂酰胺1. 2克,放入油浴中,搅拌下加热至80°C,并通氮处理0. 5小时;再加入二月桂酸二丁基锡的甲苯溶液(含二月桂酸二丁基锡0. 1克、甲苯3克)、甲苯M克及六亚甲基二异氰酸酯,异氰酸酯基与步骤1)和幻中所有反应物的总羟基的摩尔比为1.05 : 1,在氮气保护和120°C下反应3小时,制得预聚物溶液。 [0048] 1) In a flask was added α, [omega] terminal hydroxyl liquid polybutadiene (molecular weight of 2000, liquid at normal temperature), and 3 g N, N- dihydroxyethyl cinnamic amide 1.2 g, into oil bath was heated to 80 ° C, and nitrogen-treated 0.5 hours; dilaurate was added a toluene solution of dibutyl tin (including dibutyl tin dilaurate 0.1 g, toluene, 3 g), toluene M g and hexamethylene diisocyanate, the molar ratio of isocyanate groups in step 1), and phantom total hydroxyl groups of all reactants was 1.05: 1, the reaction for 3 hours under nitrogen and 120 ° C, to prepare the prepolymer solution .

[0049] 2)在预聚物中加入α,ω-端羟基聚对二氧环己酮(熔点100°C )5. 8克,在氮气保护和165°C下反应8小时,将反应产物溶液倒入玻璃皿中成膜,待溶剂自然挥发后真空干燥,得到光致形状记忆聚合物膜6。 [0049] 2) adding α in the prepolymer, the terminal hydroxyl groups of poly [omega], the reaction of dioxanone (m.p. 100 ° C) 5. 8 g under nitrogen and 165 ° C 8 hours, the reaction product of film-forming solution was poured into a glass dish, and dried in vacuo until natural volatile solvent, to obtain a photo-shape memory polymer film 6.

[0050] 实施例7 [0050] Example 7

[0051] 1)在烧瓶中加入α,ω-端羟基聚己二酸乙二醇一缩二乙二醇酯(常温下为粘稠液体)7.5克、α,ω-端羟基聚对苯二甲酸丁二酸丁二醇共聚酯(熔点Il(TC)的氯仿溶液(含聚对苯二甲酸丁二酸丁二醇共聚酯0. 5克、氯仿60克),和Ν,Ν_ 二羟乙基肉桂酰胺1. 95克,放入油浴中,搅拌下加热至50°C,并通氮处理0. 5小时;再加入辛酸亚锡的氯仿溶液(含辛酸亚锡0. 04克、1,4- 二氧六环3克)、六亚甲基二异氰酸酯和氯仿M克,异氰酸酯基与步骤1)和2)中所有反应物的总羟基的摩尔比为1.2 : 1,在氮气保护和60°C下反应3小时,制得预聚物溶液。 [0051] 1) In a flask was added [alpha], ω- terminal hydroxyl polyethylene adipate diethylene glycol ester 7.5 g (viscous liquid at room temperature), α, ω- terminal hydroxyl polyethylene terephthalate acid butylene succinate copolyester (m.p. Il (TC) in chloroform (butylene succinate containing polyethylene terephthalate copolyester 0.5 g, chloroform, 60 g), and Ν, Ν_ two hydroxyethyl cinnamamide 1.95 g, placed in an oil bath was heated to 50 ° C, and nitrogen-treated 0.5 hours; stannous octoate was added a chloroform solution (containing 0.04 g of stannous octoate , 1,4-dioxane 3 g), 1) the molar ratio of hexamethylene diisocyanate and M g of chloroform, and the isocyanate group of 2-hydroxy-step total) and of all reactants is 1.2: 1, in a nitrogen for 3 hours under protection and 60 ° C, to obtain a prepolymer solution.

[0052] 2)在预聚物溶液中加入4,4' - 二氨基二苯甲烷0.05克、在氮气保护和60°C下反应8小时;将反应产物溶液倒入玻璃皿中成膜,待溶剂自然挥发后真空干燥,得到光致形状记忆聚合物膜7。 [0052] 2) added to the prepolymer solution of 4,4 '- diaminodiphenylmethane 0.05 g, the reaction under nitrogen and 60 ° C 8 hours; the reaction product solution was poured into a glass dish deposition, to be after volatile solvent was naturally dried in vacuo to give a photo-shape memory polymer film 7.

[0053] 实施例8光致形状记忆效应 Light-induced shape memory effect Example 8 [0053] Embodiment

[0054] 将有效尺寸为30mmX 11. 6mmX0. Ilmm的聚合物膜1用电子拉力机以10mm/min的速率拉伸到应变为20%,在拉伸状态下保持该应变,用波长365nm的紫外光照射60分钟,撤去外力,应变为10. 8 %,形变固定率为;再用波长为254nm的紫外光照射60分钟,应变为3.4%,形变恢复率为83%。 [0054] The effective size of 30mmX 11. 6mmX0. Ilmm polymer film 1 by electronic testing machine at a rate of 10mm / min to a tensile strain of 20%, the strain remains in a stretched state, with a wavelength of 365nm UV light irradiation for 60 minutes external force is removed, the strain was 10.8%, the strain rate is fixed; then irradiated with ultraviolet light having a wavelength of 254nm for 60 minutes, 3.4% strain, the strain recovery rate of 83%.

[0055] 当初始应变为30%时,其形变固定率和形变恢复率分别为55%和77%。 [0055] When the initial strain of 30%, which is fixed strain rate and strain recovery rate of 55% and 77%, respectively. 当初始应变为50%时,其形变固定率和形变恢复率分别为52%和74%。 When the initial strain of 50%, which is fixed strain rate and strain recovery rate of 52% and 74%, respectively.

[0056] 其它聚合物进行类似测定。 [0056] Other polymers were similarly measured. 结果如下表。 The results in the table below.

[0057] 表1光致形状记忆测定结果 [0057] Table 1. The measurement results of light induced shape memory

[0058] [0058]

Figure CN101747486BD00101
Figure CN101747486BD00111

Claims (10)

  1. 1. 一种光致形状记忆聚合物,其特征在于,它是含有如下la、Ib或Ic所示的N-取代肉桂酰胺光敏结构单元的热塑性聚氨酯类多嵌段共聚物,其软段的主转变温度不高于50°C ; 它由(1)0. 5Wt%〜25wt%&N-二羟烷基肉桂酰胺、(2)90wt%〜20衬%的主转变温度不高于50°C的α,ω-端羟基聚合物A、(3)0〜5wt%的小分子扩链剂、0)0〜75wt%的玻璃化温度或熔点不低于50°C且比α,ω-端羟基聚合物A的主转变温度至少高20°C的α, ω-端羟基聚合物B和(¾ 二异氰酸酯反应而制得; An optical shape memory polymer characterized in that it contains the following la, N- shown Ib or Ic substituted cinnamic amide thermoplastic polyurethane-based photosensitive multiblock copolymer of the structural unit, which main soft segment transition temperature of not above 50 ° C;. it consists of (1) 0 5Wt% ~25wt% & N- ​​dihydroxyalkyl cinnamamide, (2) 90wt% ~20% of the main liner transition temperature of not higher than of 50 ° C α, ω- hydroxy terminal polymer a, (3) 0~5wt% small molecule chain extender, 0) 0~75wt% of the glass transition temperature or melting point of not lower than 50 ° C and the ratio of α, ω- terminal hydroxyl group α a main transition temperature of the polymer is at least of 20 ° C, ω- terminal hydroxyl group and a polymer B (¾ diisocyanate prepared by reacting;
    Figure CN101747486BC00021
    所述主转变温度为无定形聚合物的玻璃化温度或结晶性聚合物的熔融温度。 The main transition temperature is the melting temperature of the glass transition temperature of the amorphous polymer or a crystalline polymer.
  2. 2.如权利要求1所述的一种光致形状记忆聚合物,其特征在于,所述的N- 二羟烷基肉桂酰胺为N,N- 二羟乙基肉桂酰胺、N,N- 二羟异丙基肉桂酰胺或N-[2-羟基-1-(羟甲基) 乙基]-肉桂酰胺;所述的小分子扩链剂为乙二醇、1,4_ 丁二醇、2,3_ 丁二醇、二甘醇、1, 6-己二醇、环己二醇、环己烷二甲醇、苯二胺、联苯二胺、3,3' - 二甲基_4,4' -联苯二胺、3, 3' - 二氯_4,4' -联苯二胺、4,4' - 二氨基二苯甲烷、3,3' - 二甲氧基_4,4' - 二氨基二苯甲烷或3,3' - 二氯-4,4' - 二氨基二苯甲烷;所述的二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、2,2,4_三甲基己烷二异氰酸酯、2,4,4_三甲基己烷二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、甲基环己基二异氰酸酯、二环己基甲烷二异氰酸酯或四 2. one of the claims 1 photo shape memory polymer, wherein said N- dihydroxyalkyl cinnamic amide is N, N- dihydroxyethyl cinnamic amide, N, N- two cinnamic acid amide or hydroxyphenyl-isopropyl-N- [2- hydroxy-1- (hydroxymethyl) ethyl] - cinnamic amide; a small molecule chain extender is ethylene glycol, butanediol 1,4_, 2, 3_ butanediol, diethylene glycol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, p-phenylenediamine, benzidine, 3,3 '- dimethyl _4,4' - benzidine, 3, 3 '- dichloro _4,4' - benzidine, 4,4 '- diaminodiphenylmethane, 3,3' - dimethoxy _4,4 '- diaminodiphenylmethane or 3,3 '- dichloro - 4,4' - diaminodiphenylmethane; said diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 2 , 2,4_-trimethyl hexane diisocyanate, 2,4,4_ trimethyl hexane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-diisocyanate , methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate or tetra 基苯二亚甲基二异氰酸酯。 Benzene-dimethylene diisocyanate.
  3. 3.如权利要求1所述的一种光致形状记忆聚合物,其特征在于,所述的α,ω-端羟基聚合物A为主转变温度不高于50°C的且含α,ω-端羟基的聚酯、聚醚、聚硅氧烷、聚碳酸酯、聚酯酰胺、聚醚酯、聚酯碳酸酯或聚烯烃;所述的α,ω-端羟基聚合物B为玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的且含α,ω-端羟基的聚酯、聚碳酸酯、聚酯酰胺或聚烯烃。 3. one of the claims 1 photo shape memory polymer, wherein said α, ω- A terminal hydroxyl polymer-based transition temperature of not above 50 ° C and containing α, ω - terminal hydroxyl polyesters, polyethers, polysiloxanes, polycarbonates, polyester amides, polyether esters, polyester carbonate or polyolefin; the α, ω- terminal hydroxyl polymer B having a glass temperature or melting point of not lower than 50 ° C and the ratio of [alpha], [omega] the main transition temperature of the polymer terminal hydroxyl group of a is at least at 20 ° C and containing α, ω- terminal hydroxyl polyesters, polycarbonates, ester amide or a polyolefin.
  4. 4. 一种如权利要求1所述的光致形状记忆聚合物的制备方法,其特征在于,包括如下步骤:1)将0. 5wt%〜25衬%的^二羟烷基肉桂酰胺、90衬%〜20衬%的主转变温度不高于50°C的α,ω-端羟基聚合物A和二异氰酸酯在0〜的催化剂存在下在50_180°C下反应,异氰酸酯基与步骤1)和幻中所有反应物的羟基和氨基之和的摩尔比为1〜1.2 : 1, 制得预聚物;2)将预聚物与0. 5〜5wt%的小分子扩链剂或5〜75wt%的玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的α,ω-端羟基聚合物B在50-180°C下反应,制得光致形状记忆聚合物。 4. A method of preparing a photo-shape memory polymer according to claim 1, characterized in that it comprises the following steps: 1) The lining 0. 5wt% ~25% of cinnamic amide ^ dihydroxyalkyl, 90 % ~ 20% of the liner lining the main transition temperature of the α 50 ° C, [omega] a polymer terminal hydroxyl group and a diisocyanate in the presence of a catalyst at 0~ 50_180 ° C the reaction, the isocyanate groups in step 1) and the molar ratio of hydroxyl and amino groups of phantom all reactants and is 1~1.2: 1, to obtain a prepolymer; 2) the prepolymer 0. 5~5wt% small molecule chain extender, or 5~75wt % of the glass transition temperature or melting point of not lower than 50 ° C and the ratio of [alpha], [omega] the main transition temperature of the polymer terminal hydroxyl group of a is at least of α 20 ° C, ω- terminal hydroxyl group in the polymer B 50-180 reaction ° C, to obtain a photo-shape memory polymer.
  5. 5. 一种如权利要求1所述的光致形状记忆聚合物的制备方法,其特征在于,包括如下步骤:1)将0. 5wt%〜 二羟烷基肉桂酰胺、90wt%〜 20wt%的主转变温度不高于50°C的α,ω-端羟基聚合物Α、5〜75wt%的玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的α,ω-端羟基聚合物B和二异氰酸酯在0〜的催化剂存在下在50〜180°C下反应,异氰酸酯基与步骤1)和幻中所有反应物的羟基和氨基之和的摩尔比为1〜1. 2 : 1,制得预聚物;2)将预聚物与0. 5〜5wt%的小分子扩链剂在50-180°C下反应,制得所述的光致形状记忆聚合物。 5. A method of preparing a photo-shape memory polymer according to claim 1, characterized in that it comprises the following steps: 1) 0. 5wt% ~ dihydroxy cinnamic amide group, 90wt% ~ 20wt% of the main transition temperature of the α 50 ° C, ω- terminal hydroxyl polymer Α, 5~75wt% of the glass transition temperature or melting point of not lower than 50 ° C and the ratio of the α, ω- hydroxy terminal polymer a α main transition temperature of at least a high of 20 ° C, [omega] B terminal hydroxyl polymer and a diisocyanate in the presence of a catalyst 0~ at 50~180 ° C the reaction, the isocyanate groups in step 1) and all reactants magic the molar ratio of the sum of hydroxyl and amino groups of 1~1 2: 1, to obtain a prepolymer; 2) the prepolymer 0. 5~5wt% small molecule chain extender, at 50-180 ° C. the reaction to prepare the photo-shape memory polymer.
  6. 6. 一种如权利要求1所述的光致形状记忆聚合物的制备方法,其特征在于将0. 5wt %〜25wt %的N- 二羟烷基肉桂酰胺、90wt %〜20wt %的主转变温度不高于50°C的α,ω-端羟基聚合物A和二异氰酸酯直接在0〜Iwt%的催化剂存在下在50-180°C下反应,异氰酸酯基与反应物总的羟基的摩尔比为1〜1. 2 : 1,制得所述的光致形状记忆聚合物。 6. A method of preparing a photo-shape memory polymer according to claim 1, characterized in that 0. 5wt% ~25wt% of cinnamic acid amide N- dihydroxyalkyl, 90wt% ~20wt% primary transition temperature not higher than the molar ratio of α 50 ° C, the total direct ω- hydroxy terminal hydroxyl polymer a and a diisocyanate in the presence of a catalyst 0~Iwt% of the reaction at 50-180 ° C, the isocyanate groups with reactants 2 is 1~1: 1, to obtain the photo-shape memory polymer.
  7. 7.如权利要求4、5或6所述的一种光致形状记忆聚合物的制备方法,其特征在于,所述的N- 二羟烷基肉桂酰胺为N,N- 二羟乙基肉桂酰胺、N,N- 二羟异丙基肉桂酰胺或N-[2-羟基-1-(羟甲基)乙基]-肉桂酰胺;所述的小分子扩链剂为乙二醇、1,4_ 丁二醇、2,3_ 丁二醇、二甘醇、1,6_己二醇、环己二醇、环己烷二甲醇、苯二胺、联苯二胺、3,3' - 二甲基-4, 4' -联苯二胺、3,3' - 二氯-4,4' -联苯二胺、4,4' - 二氨基二苯甲烷、3,3' -二甲氧基_4, 4' - 二氨基二苯甲烷或3,3' - 二氯_4,4' - 二氨基二苯甲烷;所述的二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、2,2,4_三甲基己烷二异氰酸酯或2,4,4_三甲基己烷二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、甲基环己基二异氰酸酯、二环己基甲烷 7. An 4, 5 or claim 6 Preparation photoinduced shape memory polymer, wherein said N- dihydroxyalkyl cinnamic amide is N, N- dihydroxyethyl cinnamon amide, N, N- isopropyl-dihydroxy cinnamic acid amide or N- [2- hydroxy-1- (hydroxymethyl) ethyl] - cinnamic amide; a small molecule chain extender is ethylene glycol, 1, 4_ butanediol, 2,3_-butanediol, diethylene glycol, 1,6_ hexanediol, cyclohexanediol, cyclohexanedimethanol, p-phenylenediamine, benzidine, 3,3 '- bis methyl-4, 4 '- biphenyl diamine, 3,3' - dichloro - 4,4 '- biphenyl diamine, 4,4' - diaminodiphenylmethane, 3,3 '- dimethoxy _4-yl, 4 '- diamino diphenyl methane or 3,3' - dichloro _4,4 '- diaminodiphenylmethane; said diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, six methylene diisocyanate, 2,2,4_ trimethyl hexane diisocyanate or 2,4,4_ trimethyl hexane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene 1,5-diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyl methane 异氰酸酯或四甲基苯二亚甲基二异氰酸酯;所述的催化剂为辛酸亚锡、二月桂酸二丁基锡。 Tetramethylxylylene diisocyanate or dimethylene diisocyanate; the catalyst is stannous octoate, dibutyl tin dilaurate.
  8. 8.如权利要求4、5或6所述的一种光致形状记忆聚合物的制备方法,其特征在于,所述的α,ω-端羟基聚合物A为主转变温度不高于50°C的且含α,ω-端羟基的聚酯、聚醚、 聚硅氧烷、聚碳酸酯、聚酯酰胺、聚醚酯、聚酯碳酸酯或聚烯烃;所述的α,ω-端羟基聚合物B为玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的且含α,ω-端羟基的聚酯、聚碳酸酯、聚酯酰胺或聚烯烃。 8. An 4, 5 or claim 6 Preparation photoinduced shape memory polymer, wherein said α, ω- A terminal hydroxyl polymer-based transition temperature not higher than 50 ° C and containing α, ω- terminal hydroxyl polyesters, polyethers, polysiloxanes, polycarbonates, polyester amides, polyether esters, polyester carbonate or polyolefin; the α, ω- end B is a hydroxyl polymer glass transition temperature or melting point of not lower than 50 ° C and the ratio of [alpha], [omega] the main transition temperature of the polymer terminal hydroxyl group of a is at least at 20 ° C and containing α, ω- terminal hydroxyl poly , polycarbonate, polyester amide or a polyolefin.
  9. 9.如权利要求4、5或6所述的一种光致形状记忆聚合物的制备方法,其特征在于,所述的α,ω-端羟基聚合物A为主转变温度不高于50°C的且含α,ω-端羟基的聚己内酯、聚(三亚甲基碳酸酯)、聚丁二酸己二醇酯、聚丁二酸丁二醇酯、聚丁二酸丙二醇酯、聚丁二酸乙二醇酯、聚丁二酸一缩二乙二醇酯、聚己二酸己二醇酯、聚己二酸丁二醇酯、聚己二酸丙二醇酯、聚己二酸乙二醇酯、聚己二酸一缩二乙二醇酯或它们的共聚物;或者为主转变温度不高于50°C的且含α,ω-端羟基的聚乙二醇、聚丙二醇、聚四氢呋喃和它们的共聚物;或者为主转变温度不高于50°C的且含α,ω-端羟基的聚丁二烯、聚异戊二烯或丁二烯-丙烯腈共聚物。 9. An 4, 5 or claim 6 Preparation photoinduced shape memory polymer, wherein said α, ω- A terminal hydroxyl polymer-based transition temperature not higher than 50 ° C and containing α, ω- terminal hydroxy polycaprolactone, poly (trimethylene carbonate), polyethylene succinate, hexanediol diacrylate, polybutylene succinate, polybutylene succinate, propylene glycol, polyethylene succinate, polyethylene succinate, diethylene glycol, polyethylene adipate, polybutylene adipate, polypropylene adipate, polyethylene adipate ethylene glycol, diethylene glycol polyadipate esters or copolymers thereof; or the main transition temperature of not above 50 ° C and containing α, ω- terminal hydroxyl group of polyethylene glycol, polypropylene glycol , polytetrahydrofuran and copolymers thereof; or the main transition temperature of not above 50 ° C and containing α, ω- terminal hydroxyl polybutadiene, polyisoprene or polybutadiene - acrylonitrile copolymers.
  10. 10.如权利要求4、5或6所述的一种光致形状记忆聚合物的制备方法,其特征在于,所述的α,ω-端羟基聚合物B为玻璃化温度或熔点不低于50°C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20°C的且含α,ω-端羟基的聚乳酸、聚羟基乙酸、聚对二氧环己酮、聚丁二酸丁二醇酯、聚丁二酸乙二醇酯、聚己二酸丁二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸环己烷二甲醇酯或它们的共聚物。 10. An 4, 5 or claim 6 Preparation photoinduced shape memory polymer, wherein said α, ω- terminal hydroxyl polymer B or a glass transition temperature not lower than the melting point 50 ° C and the ratio of [alpha], [omega] the main transition temperature of the polymer terminal hydroxyl group of a is at least at 20 ° C and containing α, ω- terminal hydroxyl group of polylactic acid, polyglycolic acid, poly-p-dioxanone , polybutylene succinate, polyethylene succinate, polybutylene adipate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, polyethylene propylene terephthalate, polyethylene terephthalate, cyclohexane dimethanol esters or copolymers thereof.
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