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Publication numberCN101747486 B
Publication typeGrant
Application numberCN 200910156931
Publication dateSep 28, 2011
Filing dateDec 24, 2009
Priority dateDec 24, 2009
Also published asCN101747486A
Publication number200910156931.X, CN 101747486 B, CN 101747486B, CN 200910156931, CN-B-101747486, CN101747486 B, CN101747486B, CN200910156931, CN200910156931.X
Inventors吴林波, 靳春丽
Applicant浙江大学
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Light-induced shape-memory polymer and preparation method thereof
CN 101747486 B
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.
Claims(10)  translated from Chinese
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50C ; 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50C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50C且比α,ω-端羟基聚合物A的主转变温度至少高20C的α, ω-端羟基聚合物B和( 二异氰酸酯反应而制得; A light shape memory polymers, characterized in that it contains the following la, N- Ib or Ic shown substituted cinnamic amide thermoplastic polyurethane based photosensitive multiblock copolymer of the structural unit, which main soft segment transition temperature of 50 C;. It consists of (1) 0 5Wt% ~25wt% & N- dihydroxyalkyl cinnamamide, (2) 90wt% ~20% of lining a main transition temperature is not above 50 C in 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- hydroxy end A main transition temperature of the polymer is at least 20 C of α, ω- terminal hydroxyl polymer B and ( diisocyanate reactions in the system;
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 of the melting temperature of the glass transition temperature of the amorphous polymer or a crystalline polymer.
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甲基苯二亚甲基二异氰酸酯。 2. A light according to claim 1, wherein the shape memory polymer, wherein said hydroxyalkyl N- di cinnamic amide N, N- bis-hydroxyethyl cinnamic acid 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, phenylene diamine, benzidine, 3,3 '- dimethyl _4,4' - benzidine, 3, 3 '- dichloro _4,4' - biphenyl diamine, 4,4 '- diaminodiphenylmethane, 3,3' - dimethoxy _4,4 '- diaminodiphenylmethane or 3,3 - dichloro-4,4 '- diaminodiphenylmethane; said diisocyanate is toluene diisocyanate, diphenyl methane 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 tetramethylxylylene two methylene diisocyanate.
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50C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50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C的且含α,ω-端羟基的聚酯、聚碳酸酯、聚酯酰胺或聚烯烃。 3. A claim 1, wherein the light-induced shape-memory polymer, wherein said α, ω- terminal hydroxyl polymer A main transition temperature is not above 50 C and containing the α, ω - the terminal hydroxyl polyesters, polyethers, polysiloxanes, polycarbonates, polyesteramides, polyether esters, polyester carbonate or polyolefin; wherein α, ω- hydroxy terminal Polymer B as the glass temperature or melting point of not lower than 50 C and the ratio of the α, ω- main transition temperature of the polymer terminal hydroxyl group of A is at least 20 C and containing the α, ω- terminal hydroxyl polyesters, polycarbonates, ester amide or a polyolefin.
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50C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_180C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50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C的α,ω-端羟基聚合物B在50-180C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 di ^ hydroxyalkyl cinnamide, 90 lining lining% ~ 20% of the main transition temperature is not above 50 C the α, ω- terminal hydroxyl polymer A and a diisocyanate in the presence of a catalyst 0~ 50_180 C in the reaction, an isocyanate group and step 1) and The molar ratio of the reactants magic all of the hydroxyl and amino groups and is 1~1.2: 1, to obtain a prepolymer; 2) the prepolymer and 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- main transition temperature of the polymer terminal hydroxyl group of A is at least 20 C the α, ω- terminal hydroxyl polymer B in 50-180 C and response system in light-induced shape-memory polymer.
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50C的α,ω-端羟基聚合物Α、5〜75wt%的玻璃化温度或熔点不低于50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C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50〜180C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50-180C下反应,制得所述的光致形状记忆聚合物。 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 not above 50 C the α, 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 said α, ω- terminal hydroxyl polymer A at least a high transition temperature 20 C Main of α, ω- terminal hydroxyl polymer B and a diisocyanate in the presence of a catalyst 0~ 50~180 C in the reaction, an isocyanate group and step 1) and the magic of all the reactants The molar ratio of the sum of the hydroxyl group and an amino group of 1~1 2: 1 to obtain a prepolymer; 2) the prepolymer and 0. 5~5wt% of small molecule chain extender at 50-180 C lower. The reaction to prepare the light-induced shape-memory polymer.
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50C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50-180C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 N- di hydroxyalkyl cinnamamide, 90wt% ~20wt% primary transition the temperature is not above 50 C the α, ω- terminal hydroxyl polymer A and a diisocyanate in the presence of a catalyst 0~Iwt% at 50-180 C under total direct reaction of hydroxyl groups, isocyanate groups and molar ratio of reactants as 1~1 2: 1, to prepare the photochromic shape memory polymer.
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。 4, 5, 6 or 7. A claim according photocurable preparing a shape memory polymer, wherein said hydroxyalkyl N- di cinnamic amide N, N- bis-hydroxyethyl cinnamate amide, N, N- isopropyl-dihydroxy cinnamic acid amide or N- [2- hydroxy-1- (hydroxymethyl) ethyl] - cinnamic amide; wherein the small molecule chain extender is ethylene glycol, 1, 4_ butanediol, 2,3_-butanediol, diethylene glycol, 1,6_ hexanediol, cyclohexanediol, cyclohexanedimethanol, phenylene diamine, benzidine, 3,3 '- bis methyl-4, 4 '- biphenyl diamine, 3,3' - dichloro - 4,4 '- biphenyl diamine, 4,4' - diaminodiphenylmethane, 3,3 '- dimethoxy- _4 group, 4 '- diaminodiphenyl methane or 3,3 - dichloro _4,4' - diaminodiphenylmethane; said diisocyanate is toluene diisocyanate, diphenyl methane 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, dicyclohexylmethane diisocyanate or tetramethylxylylene dimethylene diisocyanate; said catalyst is stannous octoate, dibutyl tin.
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50C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50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C的且含α,ω-端羟基的聚酯、聚碳酸酯、聚酯酰胺或聚烯烃。 8. A 4, 5 or 6, wherein the preparation of claim photocurable shape memory polymer, wherein said α, ω- hydroxy terminal Polymer A main transition temperature not higher than 50 C and containing the α, ω- terminal hydroxyl polyesters, polyethers, polysiloxanes, polycarbonates, polyesteramides, polyether esters, polyester carbonate or polyolefin; wherein 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 the α, ω- main transition temperature of the polymer terminal hydroxyl group of A is at least 20 C and containing the α, ω- terminal hydroxyl groups of poly esters, polycarbonate, polyester amide or a polyolefin.
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50C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50C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50C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. A 4, 5 or 6, wherein the preparation of claim photocurable shape memory polymer, wherein said α, ω- hydroxy terminal Polymer A main transition temperature not higher than 50 C and containing the α, ω- terminal hydroxy polycaprolactone, poly (trimethylene carbonate), polyethylene glycol hexyl succinate, polybutylene succinate, polybutylene succinate, propylene glycol, polyethylene succinate, polyethylene succinate, diethylene glycol, polyethylene adipate glycol, polybutylene adipate, polypropylene adipate, polypropylene adipate polyethylene terephthalate, polybutylene adipate diethylene glycol ester or copolymer thereof; or main transition temperature is not above 50 C and containing the α, ω- terminal hydroxyl polyethylene glycol, polypropylene glycol , polytetrahydrofuran and copolymers thereof; or main transition temperature is not above 50 C and containing the α, ω- terminal hydroxyl polybutadiene, polyisoprene or polybutadiene - acrylonitrile copolymer.
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50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C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. A 4, 5 or 6, wherein the preparation of claim photocurable shape memory polymer, wherein said α, ω- hydroxy terminal Polymer B as the glass transition temperature or melting point of not lower than 50 C and the ratio of the α, ω- main transition temperature of the polymer terminal hydroxyl group of A is at least 20 C and containing the α, ω- terminal hydroxy group of polylactic acid, polyglycolic acid, poly dioxanone , polybutylene succinate, polyethylene succinate, polybutylene adipate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, polyethylene trimethylene terephthalate, polyethylene terephthalate cyclohexanedimethanol ester or a copolymer thereof.
Description  translated from Chinese

一种光致形状记忆聚合物及其制备方法 A light-induced shape-memory polymer and preparation method

技术领域 Technical 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 a functional polymer material and preparation method, particularly to a light-induced shape-memory polymer and preparation method.

背景技术 Background

[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 or intelligent polymer, when the initial shape of the molding obtained by secondary processing into a temporary shape, it "remembers" initial shape, and stimulating effect in the outside world Under recover initial 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 connecting member, 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。 Shape memory polymers, biodegradable shape memory polymer degradation due both absorbent and shape memory capabilities can also be used as medical implant materials and drug controlled release carrier, such as medical sutures, implants prevent restenosis pipe stents, vascular anastomoses / banding, tendon fixation, bone fixation. 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;(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 the shape memory alloy (SMA), a biodegradable shape memory polymer has the following advantages: (1) strain capacity, up to 100%, while only 8% of SMA; (2) a biodegradable, postoperative do not remove, patients can avoid the painful second surgery; C3) MRI acceptable; and (4) of the adjoining tissue of oppression less damage; ( convenient processing, temporary shape can be made small-sized, 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 polymers, the triggering of the shape memory effect means there are a variety of external stimuli, such as heat, light, electricity, magnetism, and even absorb water 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 (or thermally induced shape-memory) is the focus of current research and development, 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) and other reports. 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。 2005, "Nature" 034 Volume 14, P879_88 "magazine reported two non-biodegradable shape memory polymer photoluminescence. 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 prepared by radical copolymerization of photosensitive group-containing radical crosslinking copolymer and interpenetrating polymer networks prepared by interpenetrating network process photosensitive compound containing a star. 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。 After molding of the device by an external force at room temperature, after ultraviolet light wavelengths greater than 260 nm, the deformation part fixed, the other wavelengths less than 260 nm ultraviolet light, 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 thermal shape memory effect, light-induced shape-memory effect can be excited by UV over a wide temperature range, there is no strong temperature dependence, and the use of non-surface portion of the optical fiber and other means for remote excitation . 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 features are very advantageous for certain applications, such as in medical clinical application when heated to high temperatures to avoid discomfort, especially remote stimulate beneficial 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。 Therefore, not only to research and development of light-induced non-degradable shape memory polymer, it is necessary photocurable synthetic biodegradable shape memory polymer absorption. 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。 With the biodegradable shape memory polymer and thermal non-biodegradable shape memory polymer light compared to making a biodegradable shape memory polymer light is much more difficult, is still basically stuck 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] Therefore, the research and development of new light-induced shape-memory polymer and preparation methods, especially light biodegradable shape memory polymer and preparation methods, especially for the preparation of simultaneous non-degradable and biodegradable light shape memory polymers, or issues to be resolved techniques. 发明内容 DISCLOSURE

[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 to overcome the deficiencies of the prior art and to provide a light-induced shape-memory polymer and preparation method.

[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50C ;它由(l)0.5Wt%〜 [0007] photoinduced shape memory polymer containing the following la, N- lb or Ic shown 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 consists of (l) 0.5Wt% ~

二羟烷基肉桂酰胺、(2)90wt%〜 20wt%的主转变温度不高于50C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50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C的α,ω-端羟基 Dihydroxy cinnamic amide group, (2) 90wt% ~ 20wt% of the main transition temperature of not higher than 50 C the α, 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 the α, ω- main transition temperature of the polymer terminal hydroxyl group of A is at least 20 C the α, ω- hydroxy end

聚合物B和(5) [0008] Polymer B and (5) [0008]

:异氰酸酯反应而制得; : Isocyanate-reactive in the system;

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 of preparing a photo-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50C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50-180C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% ~ dihydroxyalkyl cinnamamide, 90wt% ~ 20wt% of the main transition temperature is not above 50 C the α, ω- terminal hydroxyl polymer A and a diisocyanate in 0~ of presence of a catalyst at 50-180 C reaction, the isocyanate groups in step 1) and 2), all reactants of hydroxyl and amino and the molar ratio of 1~1.2: 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50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C的α,ω-端羟基聚合物B在50-180C下反应,制得光致形状记忆聚合物。 [0011] 2) the prepolymer and 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 a main transition temperature of the polymer is at least 20 C in the A α, ω- terminal hydroxyl polymer B at 50-180 C reaction to prepare light 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50C的α,ω-端羟基聚合物Α、5〜75wt%的玻璃化温度或熔点不低于50C且比所述的α,ω-端羟基聚合物A的主转变温度至少高20C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50〜180C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) 0. 5wt% ~25% of N- lining dihydroxyalkyl cinnamamide, 90wt% ~ 20wt% of the main transition temperature is not above 50 C the α, 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- main transition temperature of the polymer terminal hydroxyl group of A is at least 20 C the α, ω- terminal hydroxyl group and polymer B diisocyanate in the presence of a catalyst at 50~180 C 0~ reacting isocyanate groups in step 1) the molar ratio of 2), and all of the reactants and the hydroxyl group and an amino group of 2 to 1~1: 1, the system prepolymers;

[0014] 2)将预聚物与0. 5〜5wt%的小分子扩链剂在50_180C下反应,制得所述的光致形状记忆聚合物。 [0014] 2) the prepolymer and 0. 5~5wt% of small molecule chain extender reaction 50_180 C lower, to prepare the light-induced shape-memory polymer.

[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50C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50-180C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: 0. 5wt% ~25wt% of N- di hydroxyalkyl cinnamamide, 90wt% ~20wt% of the main transition temperature of not higher than 50 C The α, ω - A molar ratio of terminal hydroxyl polymer and a diisocyanate directly in the presence of a catalyst at 50-180 C 0~ reacting an isocyanate group with a total of hydroxyl groups 1~1.2: 1, to prepare the light-induced 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] N- said two hydroxyalkyl cinnamic amide N, N- dihydroxyethyl cinnamic acid 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, phenylene diamine, benzidine, 3, 3 '- dimethyl base _4,4 '- biphenyl diamine, 3,3 - dichloro _4,4' - biphenyl diamine, 4,4 '- diaminodiphenylmethane, 3, 3' - dimethoxy _4,4 '- diaminodiphenyl methane or 3,3 - dichloro _4,4' - diaminodiphenylmethane; said diisocyanate is toluene diisocyanate, diphenyl methane 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 dimethylene diisocyanate; said catalyst is stannous octoate, dibutyl tin.

[0017] 所述的α,ω-端羟基聚合物A为主转变温度不高于50C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50C且比所述的α,ω-端羟基聚合物A 的主转变温度至少高20C的且含α,ω-端羟基的聚酯、聚碳酸酯、聚酯酰胺或聚烯烃。 Α [0017] wherein, ω- terminal hydroxyl polymer A main transition temperature not higher than 50 C and containing the α, ω- hydroxy terminal polyester, polyether, polysiloxane, polycarbonate, polyester amides, polyether esters, polyester carbonate or polyolefin; wherein α, ω- terminal hydroxyl polymer B as the glass transition temperature or melting point of not lower than 50 C and the ratio of the α, ω- end transition temperature at least high primary hydroxyl polymer A is 20 C and containing the α, ω- terminal hydroxyl polyesters, polycarbonates, polyester amide or a polyolefin.

[0018] 所述的α,ω-端羟基聚合物A为主转变温度不高于50C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50C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50C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], wherein the α, ω- terminal hydroxyl polymer A main transition temperature is not above 50 C and containing the α, ω- terminal hydroxyl polycaprolactone, poly (trimethylene carbonate), poly succinate, hexanediol diacrylate, polybutylene succinate, polybutylene succinate, propylene glycol, polyethylene succinate, polybutylene succinate diethylene glycol, polyethylene adipate or main transition; glycol, polybutylene adipate, polypropylene adipate, polyethylene adipate, polybutylene adipate diethylene glycol ester or a copolymer thereof the temperature is not above 50 C and containing the α, ω- terminal hydroxyl polyethylene glycol, polypropylene glycol, polytetrahydrofuran and copolymers thereof; or main transition temperature not above 50 C and containing the 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50C且比所述的α, ω-端羟基聚合物A的主转变温度至少高20C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] wherein, ω- terminal hydroxyl polymer B as the glass transition temperature or melting point of not lower than 50 C and the ratio of the α, ω- terminal hydroxyl polymer A main transition temperature is at least 20 C and containing the α, ω- terminal hydroxyl polylactic acid, polyglycolic acid, poly-p-dioxanone, polybutylene succinate, polyethylene succinate, polybutylene adipate ester, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate cyclohexanedimethanol 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 of the present invention provides N- substituted cinnamic amide containing structural units of the photosensitive multiblock copolymer thermoplastic urethanes, good moldability, and at a temperature within a wide range by UV excitation, there is no strong temperature dependence; optical fiber and other means can be used for remote parts of the non-surface 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 light-induced shape-memory polymer provided by the invention can not be light-induced degradation of the shape memory polymer, but also light biodegradable shape memory polymers segment by changing the structure of the multi-block copolymer to adjust its biodegradability and other properties to meet in the use of the mechanical properties and degradation rate requirements.

[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 light biodegradable shape memory polymers can be avoided in the clinical application of the sensitivity of the temperature of the hot shape memory inconvenience and discomfort heated to high temperatures; can also be used Remote stimulate the body to achieve the characteristics of shape recovery, 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 preparation method of light-induced shape-memory polymer of the present invention provides a simple and practical, versatile, both for the preparation of light-induced shape-memory biodegradable polymer, can also be used for non-degradable shape memory polymer photoluminescence preparation, is conducive to 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 light-induced shape-memory polymer 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 ^ a polycaprolactone and polylactic acid ester group absorption, 1603CHT1 and 1649cm-1 is a structural unit of the photosensitive benzene and CH = CH absorption double bond; [0025] Figure 2 is a photo-shape memory polymer 1H NMR Nmr 1 .6 8-7 6ppm as cinnamoyl group and the benzene ring double bond CH = CH chemical shift;... 1-1 5ppm and 5. Oppm of polymer segments in the chemical shift CH3 and CH; the other is polycaprolactone and attachment unit chemical shift of hydrogen atoms.

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。 Light-induced shape-memory polymer provided by the invention [0026] The N- substituted cinnamic amide containing photosensitive structural unit, thermoplastic urethane-based soft segment and hard segment multiblock polymers. 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50C ;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50C且比软段的主转变温度至少高20C,硬段能形成物理交联结构。 Its soft segment A segment is a polymer (hereinafter referred to as segment A), main soft segment transition temperature (transition temperature of the primary glass transition temperature of the amorphous polymer or a crystalline polymer melting temperature) of not higher than 50 C; hard segment for two or two urea urethane structural units, or two by two urethane or urea structural units and small molecule chain extender residues constitute a hard segment, or two by two urethane or urea structural units of the polymer B segment (hereinafter referred to as the B segment) together constitute the hard segment, the glass transition temperature or the melting point of the hard segment is not less than 50 C and at least a higher temperature than the main soft segment transition 20 C, 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] The present invention, when only the A segment and B segment and no A segment is a biodegradable segment, or segments containing both A and B segments, and when they are biodegradable segment, this The invention provides a photoinduced shape memory polymer is biodegradable shape memory polymer; when only segment A and segment B and not A segment is non-biodegradable segment or segments containing both A and B segment and when they are non-biodegradable segment, the present invention provides a light-induced shape-memory polymer is non-biodegradable shape memory polymer; when the segment contains both A and B segment and there is one and only one of them is When the biodegradable segments, photochromic polymers of the present invention is to provide a shape memory portion for 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] In the external force, the polymer is deformed, while ultraviolet light wavelengths greater than 260 nm, the photosensitive structural unit cycloaddition reaction to produce additional light-induced cross-linking structure, the polymer can be maintained or part of the holding temporary deformed shape; in another wavelength ultraviolet light less than 260 nm when light-induced cross-linking structure use to unlock and restore its initial 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] The present invention, the light-induced shape-memory polymer using N- dihydroxyalkyl cinnamamide a photosensitive monomer, α, ω- terminal hydroxyl polymer chain extension agents and small molecule diisocyanate obtained by the reaction, preparation Similar to traditional polyurethane preparation method is 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。 A photosensitive monomer, α, ω- hydroxy terminal polymers A and B, both small molecule chain extender containing active hydrogen (a hydroxyl group or an amino group) of the reactant, an amount based on the total mass of all active hydrogen reactant (i.e., light-sensitive monomers, α, ω- terminal hydroxyl polymers A and B, a small molecule chain extender and) percent. 制备时可不加催化剂,也可加入聚氨酯合成的常用催化剂。 The preparation of a catalyst may also be added to conventional catalysts of polyurethane synthetic. 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 light, can be certified by the FDA stannous octoate as a catalyst to ensure that the product excellent biocompatibility. 催化剂用量为所有含活泼氢反应物总质量的0〜lwt%。 Catalyst for all of the active hydrogen containing reactant total mass 0~lwt%. 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 of the following control: the molar ratio of isocyanate groups with all reactant hydroxy and amino sum of 1~1 2: 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, the use of ultraviolet lamps installation of electronic materials testing machine, experimental determination of mechanical circulatory light by light-induced shape memory effect. 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 is lOmm / min speed stretched to strain ε m; while maintaining the strain unchanged, the sample in a certain light intensity of ultraviolet light having a wavelength of a certain time, the removal of the external force, measured with a vernier caliper without stress % strain conditions, according to ε u / ε m fixed rate & calculation strain; then, the sample was a certain wavelength of the light intensity of ultraviolet light some time, measurement of residual strain% by Rr = (^ - ^ Shu / ^ strain recovery rate calculated Burgundy.

[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] The 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80C,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80〜85C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- bis-hydroxyethyl cinnamamide O. 5 g) and 1,4_ dioxane M g, placed in an oil bath was heated to 80 C, and nitrogen processing 0.5 hours; then add 0. 2wt% of stannous tin and hexamethylene diisocyanate, an isocyanate group Step 1) molar ratio) and the total of all reactant hydroxy of 1.1: 1, reaction three hours in a nitrogen atmosphere and 80~85 C, the prepared prepolymer solution.

[0034] 2)在预聚物溶液中加入α,ω -端羟基聚L-乳酸(熔点170C,4. 4克)、1,4_ 二氧六环55. 6克,在氮气保护和80〜85C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 L- polylactic acid (m.p. 170 C, 4 4 g), 1,4_ dioxane 55.6 g, in nitrogen atmosphere and The reaction 80~85 C for 6 hours; the reaction product solution was poured into a glass dish and a film-forming, and dried under vacuum until the solvent natural evaporation, to obtain photoinduced shape memory polymer film 1.

[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50C,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50C下反应8小时,制得预聚物溶液; [0036] 1) In a flask, α, ω- end hydroxyl liquid polycaprolactone (molecular weight of 530,1. 5 g) and Ν, Ν_ diethylol cinnamic amide (1.0 g), into the oil bath was heated to 50 C, and nitrogen processing 0.5 hours; then adding hexamethylene diisocyanate and 1,4_ dioxane M g, an isocyanate group and step 1) and magic in all reactions The molar ratio of the total hydroxyl groups was 1.1: 1, 8 hours in a nitrogen atmosphere and at 50 C to obtain a prepolymer solution;

[0037] 2)在预聚物溶液中加入α,ω-端羟基聚L-乳酸(熔点170C,7.5克),在氮气保护和80〜85C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, ω- terminal hydroxyl groups of poly-lactic acid L- (m.p. 170 C, 7.5 g) was reacted in a nitrogen atmosphere and 80~85 C for 6 hours; the reaction product solution It was poured into a glass dish in a film after the solvents volatilize naturally dried in vacuo to give a light shape memory polymer film 2.

[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25C )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80C,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80〜85C下反应3小时,制得预聚物溶液。 [0039] 1) In a flask was added α, ω- terminal hydroxy polycaprolactone - glycolide copolymer (molecular weight of 2,000, a melting point of about 25 C) 8 克 and N- [2- hydroxy-1- (hydroxymethyl methyl) ethyl] - cinnamide 1.5 g, placed in an oil bath and heated with stirring to 80 C, and the nitrogen treated 0.5 hours; then was added a toluene solution of stannous octoate (stannous octoate containing 0.04 g, toluene, 4 g), toluene M g and toluene diisocyanate, isocyanate groups in step 1) the molar ratio of 2) and all reactants hydroxyl groups is 1: 1, in a nitrogen atmosphere and 80~85 Reaction C for 3 hours 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80〜85C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) was added to the prepolymer solution 1,4_ butanediol 0.5 g, reaction in nitrogen and 80~85 C for 6 hours; the reaction product solution is poured into a glass dish in a film, to be After the volatile solvent naturally dried in vacuo to give a light 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50C)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80C,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80〜85C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, ω- terminal hydroxy polyethylene glycol adipate glycol copolyester (waxy solid at room temperature, not more than a melting point of 50 C) 9 克 and Ν, Ν- dihydroxyethyl cinnamamide 1 g, placed in an oil bath was heated to 80 C, and nitrogen for 0.5 hours; then add toluene M g and diphenyl methane diisocyanate, an isocyanate group and step 1) and 2) All The molar ratio of total hydroxyl groups of the reactants is 1.1: 1, and reacted at 80~85 C nitrogen atmosphere for 8 hours; the reaction product solution was poured into a glass dish and a film-forming, and dried under vacuum until the solvent natural evaporation to give light-induced shape-memory polymer film 4.

[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180C,并通氮处理0.5小时;冷却至100C,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50C下反应3小时,制得预聚物。 [0044] 1) was added to the flask α, ω - terminal hydroxyl liquid polydimethylsiloxane 2 g and N, N- bis-hydroxyethyl cinnamamide 0.05 g, placed in an oil bath and heated with stirring to 180 C, and nitrogen for 0.5 hours; cooled to 100 C, then add toluene diisocyanate, a molar ratio of isocyanate groups with all reactants hydroxyl groups of 1.1: 1, the reaction in a nitrogen atmosphere and at 50 C 3 hours, to obtain 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160C )7. 95克,在氮气保护和180C下反应3小时,得到光致形状记忆聚合物5。 [0045] 2) adding α in the prepolymer, ω- terminated poly (butylene terephthalate) (molecular weight of about 2,000, a melting point of about 160 C) 7. 95 grams of nitrogen and 180 C under protection for 3 hours to obtain a photo-shape memory polymer 5. [0046] 聚合物5经热压,得到片材。 [0046] Polymer 5 by hot pressing 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80C,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120C下反应3小时,制得预聚物溶液。 [0048] 1) In a flask was added α, ω- terminal hydroxyl liquid polybutadiene (molecular weight of 2000, liquid at normal temperature) 3 g and N, N- bis-hydroxyethyl cinnamic amide 1.2 g, into oil bath with stirring and heated to 80 C, and the nitrogen treated 0.5 hours; then was added a solution of di-butyl tin dilaurate in xylene (containing 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 the magic of the hydroxyl groups of all reactants is 1.05: 1, the reaction for 3 hours in a nitrogen atmosphere and 120 C, the prepared 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100C )5. 8克,在氮气保护和165C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, ω- terminal hydroxyl poly DIOXANONE (melting point of 100 C) 5. 8 g, reaction in nitrogen and 165 C for 8 hours, the reaction product a film-forming solution was poured into a glass dish and dried under vacuum until the solvent natural evaporation, to obtain a shape memory polymer film photo-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50C,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60C下反应3小时,制得预聚物溶液。 [0051] 1) In a flask was added α, ω- terminal hydroxyl polyethylene glycol 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 solution (containing polyethylene terephthalate copolyester (butylene succinate) 0.5 g, 60 g chloroform), and Ν, Ν_ two hydroxyethyl Cinnamamide 1.95 g, placed in an oil bath and stirred and heated to 50 C, and nitrogen processing 0.5 hours; then add chloroform solution of stannous octoate (stannous tin containing 0.04 g , 1,4-dioxane, 3 g), hexamethylene diisocyanate and chloroform M g, an isocyanate group and step 1) the molar ratio of 2) and all reactants hydroxyl groups is 1.2: 1, in a nitrogen protection and response at 60 C for 3 hours 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60C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) was added to the prepolymer solution of 4,4 '- diaminodiphenylmethane 0.05 g, reaction in a nitrogen atmosphere and 60 C for 8 hours; the reaction product solution was poured into a glass dish and a film to be After the volatile solvent naturally dried in vacuo to give a shape memory polymer film photo-7.

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

[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 the polymer film with electronic testing machine at a rate of 10mm / min are stretched to a strain of 20%, keeping the strain in the stretched state, with a wavelength of 365nm UV light irradiation 60 minutes, the external force is removed, the strain was 10.8%, the strain rate is fixed; then irradiated with ultraviolet light having a wavelength of 254nm 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%, the deformation and deformation recovery rate fixed 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%, the deformation and deformation recovery rate fixed 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 following table.

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

[0058] [0058]

Figure CN101747486BD00101
Figure CN101747486BD00111
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Non-Patent Citations
Reference
1Andreas Lendlein,et al..Light-induced shape-memory polymers.《Nature》.2005,第434卷(第7035期),第879-882页.
2袁征 等.可生物降解多嵌段聚(酯-氨酯)的合成及其热致形状记忆性质.《高分子学报》.2009,(第2期),第153-158页.
Classifications
International ClassificationC08G18/66, C08G18/65, C08G18/12, C08G18/32
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