CN103524697B - One kind of urea hydrogel and method for preparing a polyurethane - Google Patents

One kind of urea hydrogel and method for preparing a polyurethane Download PDF

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CN103524697B
CN103524697B CN201310518085.8A CN201310518085A CN103524697B CN 103524697 B CN103524697 B CN 103524697B CN 201310518085 A CN201310518085 A CN 201310518085A CN 103524697 B CN103524697 B CN 103524697B
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郭明雨
崔玉琳
檀梅
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苏州大学
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Abstract

本发明涉及一种聚氨酯脲水凝胶及其制备方法。 The present invention relates to a method for preparing a urea hydrogel and a polyurethane. 包括两种制备方法,一是在聚乙二醇(PEG)有机溶液中加入二异氰酸酯和催化剂反应,再加入扩链剂二胺,在有机溶剂中沉淀得到产物;其中,PEG︰二异氰酸酯︰二胺的摩尔比为1∶2︰1。 Preparation includes two methods, one (PEG) was added to a solution of polyethylene glycol, an organic diisocyanate and catalyst, a diamine chain extender was added, the precipitate in an organic solvent to give the product; wherein PEG︰ two diisocyanate ︰ molar ratio of amine to 1:2︰1. 二是在PEG有机溶液中加入N,N′-二羰基二咪唑反应,再加入过量的扩链剂二胺,得到两端是胺基的大分子,最后再加入二异氰酸酯,在有机溶剂中沉淀得到产物,其中,PEG︰二异氰酸酯的摩尔比为1∶2。 PEG was added in two organic solution N, N'- dicarbonyl diimidazole, then excess of diamine chain extender to give a group at both ends of a macromolecule, then add the diisocyanate and precipitated in an organic solvent the product was obtained wherein the molar ratio of diisocyanate PEG︰ is 1:2. 本发明提供的聚氨酯脲水凝胶具有伸长率大、拉伸强度高的特点,并具有形状记忆功能,在生物医用水凝胶、组织工程、水凝胶支架材料以及形状记忆功能所赋予的生物医用器件等方面具有应用前景。 Polyurethaneurea hydrogels of the present invention provides a large elongation, high tensile strength characteristics, and has a shape memory function, in biomedical hydrogels, tissue engineering, scaffolds, and the hydrogel shape memory imparted The medical device having a bio-like application.

Description

一种聚氨酯脲水凝胶及其制备方法 One kind of urea hydrogel and method for preparing a polyurethane

技术领域 FIELD

[0001] 本发明涉及生物医用高分子材料和超分子化学领域,尤其涉及一种具有优良的机械性能及可实现水或热响应性形状记忆功能的聚氨酯脲水凝胶及其制备方法。 [0001] The present invention relates to a biomedical polymer materials and supramolecular chemistry, and more particularly relates to a polyurethane excellent mechanical properties and hydrogels may be implemented and urea of ​​water or thermally responsive shape memory.

背景技术 Background technique

[0002] 水凝胶是一种在水中溶胀,但是并不能溶解的物质。 [0002] is a hydrogel swells in water but does not dissolve the substance. 过去几十年间,有大量的工作致力于水凝胶的研究,水凝胶这种材料可以广泛的应用于生物医学方面,比如,药物载体、创伤敷料、软骨的替换、人工肾脏膜及其他医学器件。 Over the past few decades, there is a lot of work dedicated to the research of the hydrogel, hydrogel material that can be widely used in biomedical aspects, such as drug delivery, wound dressings, replace cartilage, artificial kidney film and other medical devices. 但是由于水凝胶处于溶胀态时, 通常表现为弱的机械性能,所以其应用受到了很大的限制。 However, when in the swollen state since the hydrogel-usually weak mechanical properties, so its application has been very limited. 因为作为生物医用材料,除需具有一定的生物相似性和相容性外,还需具有优良的机械强度、稳定性和外力作用下的形变恢复性能。 Because, as biomedical materials, in addition to the need to have certain similarities and biological compatibility, the need to have excellent mechanical strength, stability under deformation and recovery properties of the external force. 传统的提高水凝胶机械性能的方法主要是依赖于提高化学交联点的密度,但是提高交联点通常会导致吸水率的降低,而且除去未反应的交联剂的过程很繁琐。 Traditional improve the mechanical properties of the hydrogel is mainly dependent on the method of chemical crosslinking to increase the density of points, but the increase crosslinking points often causes poor water absorption, and the process of removing unreacted crosslinker cumbersome. 由于以上这些限制,物理交联的水凝胶开始受到广泛的关注。 Because of these limitations, physically crosslinked hydrogels began to receive widespread attention. 文献(Macromolecules, 2010,43, 7637 - 7649)报道了一种水凝胶,将亲水性的聚乙二醇(PEG)软段与疏水性的P0SS硬段结合起来,二者都可以形成结晶区,硬段结晶区可以充当物理交联点,从而形成有机-无机复合网络,其剪切模量最高可达4. 0MPa,但由于其是有机-无机复合材料,因此在材料的相容性方面存在不足。 Literature (Macromolecules, 2010,43, 7637 - 7649) reported a hydrogel, hydrophilic polyethylene glycol (PEG) soft segment and the hard segment P0SS hydrophobic combine both crystallinity can be formed area, the hard segment crystalline regions may serve as physical crosslinking points, thereby forming an organic - inorganic composite web, which shear modulus of up to 4. 0MPa, but because it is an organic - inorganic composite material, and therefore the material compatibility there is lack of respect.

[0003] 聚氨酯脲水凝胶中含有氨基甲酸酯基和脲基,分子间可以形成大量的氢键,这些氢键作用力相当于一个个瞬态的交联点,从而有利于合成的水凝胶的强度的增强。 [0003] The aqueous polyurethane-urea hydrogel contains between urethane and urea groups, it can form a large number of hydrogen molecules, hydrogen bonding force which corresponds to a crosslinking point of a transient, thereby facilitating synthesis of enhance the strength of the gel. 但是由于水凝胶中含有大量的水分子,在形成氢键的过程中,水会与聚氨酯脲自身的氢键发生竞争,以至于水凝胶自身结构中的氢键数目减少,所以大多数合成的聚氨酯脲水凝胶强度很低。 However, since the hydrogel contains a large number of water molecules during the formation of hydrogen bonds, the water will itself polyurethane urea hydrogen bonds competition, so that the hydrogel to reduce the number of hydrogen bonds in the structure itself, so that most synthetic polyurethaneurea hydrogels of low intensity. 文献(Biomacromolecules, 2012,13,3966 - 3976)报道了一种依靠多重氢键与疏水作用力之间的协同作用形成的在水中很稳定的可注射的PEG-脲嵌段共聚物水凝胶,通过调节物理交联点的密度以及疏水链段的长度,其模量可以在0.4~20kPa之间进行调节。 Document (Biomacromolecules, 2012,13,3966 - 3976) reported a synergy between rely on multiple hydrogen bonding and hydrophobic interaction in the formation of very stable water injectable PEG- urea block copolymers of hydrogels, which modulus may be adjusted between 0.4 ~ 20kPa by adjusting the density and the length of the hydrophobic segment physical crosslinking point. 但是由于分子中形成的疏水聚集作用不是很强,从形态上看,这种水凝胶还是比较稀黏,难以定型,很多需要高机械强度的应用方面的因而受到限制。 However, due to the hydrophobic aggregation formed in the molecule is not very strong, the morphological point of view, such hydrogels is relatively thin sticky, difficult to style, many applications require a high mechanical strength and therefore limited.

[0004] 此外,需要植入人体的生物医用材料在使用时,怎样使得植入过程中对病人造成的创伤最小,植入之后怎样取出,也受到越来越多的关注。 [0004] In addition, the need for implanted biomedical materials in use, how to make the process of implantation trauma caused to the patient is minimal, how removed after implantation, has also been more and more attention. 形状记忆聚合物(SMPs)型人工器件恰好满足了这方面的需求。 Shape memory polymers (SMPs) type artificial devices just to meet this need. 这是因为,具有一定初始形状的SMPs制品,可在特定的加工程序下产生所需形变,制备成适合微创手术的临时形状,该临时形状植入体内后可在外界刺激(如热、光、电、磁和溶剂等)下恢复至其初始形状。 This is because, SMPs article having a certain initial shape, to produce the desired deformation at a specific processing procedure to prepare a suitable temporary shape minimally invasive surgery, the temporary shape may be implanted in the body after an external stimulus (such as heat, light the return to its original shape, electrical, magnetic and solvents). 但目前所有SMPs(包括目前已有报道的水响应性SMPs)的形变产生都需在较高的温度下(聚合物的1;或T"以上)进行,容易造成材料表面或内部的生物活性成分(如蛋白和药物等)的活性大大降低,甚至失效。同时, 目前绝大部分的SMPs为热敏型,其形变恢复也需在较高的温度下进行,易对植入部位周围的组织造成损伤。公开号为W0 2012/168392A1的PCT专利报道了一种水和热双重响应功能的形状记忆的水凝胶,其特点是将干态的水凝胶加热到70 °C,使其转变为高弹态,然后再在高弹态下设计一个瞬态形状,温度降到转变温度以下后,此临时形状被固定,然后再在水或热的刺激下恢复到初始形状的。 But all SMPs (including water-responsive SMPs have been reported current) is generated by deformation are required at higher temperatures; for (1 polymer or T "above), the active ingredient is likely to cause the biological material or the interior surface of the (such as proteins and drugs, etc.) is greatly reduced activity, or even failure. Meanwhile, most of the current SMPs thermosensitive type, which also need to be strain recovery at high temperatures, easily lead to tissue surrounding the implantation site injury. PCT Patent Publication No. W0 2012 / 168392A1 reported a shape memory in response to the double function water heat hydrogel, which is characterized by dry hydrogel was heated to 70 ° C, and turn it into elastomeric state, and then design a transient form in a high elastic state, after the temperature drops below the transition temperature, this temporary shape is fixed, and then restored to the original shape in water or heat stimulation.

发明内容 SUMMARY

[0005] 本发明所要解决的问题是克服现有技术中合成聚氨酯脲水凝胶存在的机械强度较弱的不足,提供一种合成方法简单,机械强度高,适用范围广泛,且同时具有温度和水响应的形状记忆功能,综合性能优良的聚氨酯脲水凝胶及其制备方法。 [0005] The present invention is to overcome the problem of insufficient mechanical strength is weak in the prior art synthesis polyurethaneurea hydrogels present, there is provided a synthetic method is simple, high mechanical strength, a wide range, while having a temperature and water shape memory response, excellent overall performance polyurethaneurea hydrogels their preparation.

[0006] 实现本发明的目的技术方案是提供一种聚氨酯脲水凝胶的合成方法,所述水凝胶为聚乙二醇、二异氰酸酯和二胺的共聚物,其结构式为: [0006] The object of the present invention achieve technical solution is to provide a polyurethane urea synthesis hydrogel, the hydrogel is a polyethylene glycol, a copolymer of a diisocyanate and a diamine having the formula:

Figure CN103524697BD00051

,式中,R 为二异氰酸酯中两个异氰酸根之间的烷基或芳香基,V为二胺中两个胺基之间的烷基或芳香基,/为聚乙二醇,η为聚合度。 , Wherein, R is a diisocyanate in between two isocyanate-alkyl or aryl group, V is an aromatic diamine or an alkyl group between the two group, / polyethylene glycol, [eta] is the degree of polymerization.

[0007] 以上所述的聚氨酯脲水凝胶,其拉伸的断裂伸长率为200~2000 % ;拉伸强度为10 ~2000kPa。 [0007] The above-described polyurethaneurea hydrogels, tensile elongation at break of 200 to 2000%; a tensile strength of 10 ~ 2000kPa.

[0008] 本发明提供的聚氨酯脲水凝胶基于脲基中的多重氢键以及疏水聚集协同作用的方法来增强聚氨酯脲水凝胶的强度。 [0008] The polyurethaneurea hydrogel of the invention provides ureido the multiple hydrogen bonding and a hydrophobic aggregation method based on the synergistic effect to enhance the strength polyurethaneurea hydrogel.

[0009] 本发明涉及的聚氨酯脲水凝胶的制备,可通过以下两个路线实现: Polyurethaneurea hydrogel was prepared according to the present invention [0009], can be achieved by two routes:

Figure CN103524697BD00052

[0014] 式中,R代表二异氰酸酯中两个异氰酸根之间的烷基或芳香基,W代表二胺中两个胺基之间的烷基或芳香基代表聚乙二醇(PEG),η为聚合度。 [0014] In the formula, R represents between two isocyanate or two isocyanate-alkyl aryl group, W Representative diamines alkyl group or an aromatic group represented between two polyethylene glycol (PEG) , η is the degree of polymerization.

[0015] 第一种制备方法的具体步骤如下: [0015] In particular a first step of the method is as follows:

[0016] (1)将聚乙二醇溶解于有机溶液Α中,所述有机溶剂Α为DMF、丙酮、氯仿、二氯甲烷、二氯乙烷中的一种;再加入二异氰酸酯和催化剂,所述催化剂为辛酸亚锡、二月桂酸二丁基锡、N-乙基吗啉、N-甲基吗啉、吡啶、N,f-二甲基吡啶中的一种;在温度为20 ~ 80 °C的条件下反应1 ~ 5小时,按摩尔比,聚乙二醇:二异氰酸酯为1 : 2 ; [0016] (1) Polyethylene glycol is dissolved in the organic solution Α, the organic solvent is Α as DMF, acetone, chloroform, dichloromethane, dichloroethane one; diisocyanate was added and the catalyst, the catalyst is stannous octoate, dibutyl tin dilaurate, N- ethylmorpholine, N- methylmorpholine, pyridine, N, f- lutidine one; at a temperature of 20 ~ 80 ° for 1 to 5 hours under the condition C, the molar ratio of polyethylene glycol: diisocyanate is 1: 2;

[0017] (2)加入扩链剂二胺单体,在温度为20 ~ 80 °C,氮气保护下搅拌反应1 ~ 5小时,按摩尔比,聚乙二醇:二异氰酸酯:二胺为1 : 2 : 1 ; [0017] (2) a chain extender diamine monomer is added at a temperature of 20 ~ 80 ° C, the reaction was stirred under nitrogen for 1 to 5 hours, a molar ratio of polyethylene glycol: diisocyanate: diamine is 1 : twenty one ;

[0018] (3 )反应结束后将产物置于有机溶剂B中,所述有机溶剂B为正己烷、正庚烷、异己烷、异庚烷、环己烷、乙醚中的一种,得到白色絮状固体沉淀物;干燥后再溶解于有机溶剂C 中,所述有机溶剂C为甲醇、乙醇、氯仿或二氯甲烷中的一种,倒入模具中成型,溶剂挥发晾干后,在蒸馏水中溶胀直至达到溶胀平衡,得到一种聚氨酯脲水凝胶。 [0018] (3) After the end of the reaction product was placed in an organic solvent B, B of the organic solvent is n-hexane, n-heptane, isohexane, heptane, cyclohexane, one kind of ether to give a white flocculent solid precipitate; dried again dissolved in an organic solvent C in the organic solvent C as a methanol, ethanol, chloroform or methylene chloride, poured into a mold to dry solvent evaporation in distilled water swelling until swelling equilibrium, to obtain a polyurethaneurea hydrogels.

[0019] 另一种制备聚氨酯脲水凝胶的方法的具体步骤如下: [0019] Another particular method steps polyurethaneurea hydrogel was prepared as follows:

[0020] (1)将聚乙二醇溶解于有机溶液A中,所述有机溶剂A为DMF、丙酮、氯仿、二氯甲烷、二氯乙烷中的一种;按摩尔比,再加入过量的N,N'-二羰基二咪唑,室温、氮气保护条件下充分反应,结束后将溶液在有机溶剂B中沉淀,所述有机溶剂B为正己烷、正庚烷、异己烷、异庚烷、环己烷、乙醚中的一种;将得到的白色粉状沉淀物抽滤、干燥; [0020] (1) Polyethylene glycol is dissolved in an organic solution A, the organic solvent A is as DMF, acetone, chloroform, dichloromethane, dichloroethane one; molar ratio, then adding an excess of of N, N'- under dicarbonyl diimidazole, at room temperature, nitrogen sufficient reaction conditions, the end of the solution was precipitated in an organic solvent B in the organic solvent B is n-hexane, n-heptane, isohexane, heptane , cyclohexane, diethyl ether one; the resulting white powdery precipitate was filtered off with suction and dried;

[0021] (2 )将步骤(1)得到的产物溶解在有机溶液A中,按摩尔比,加入过量的扩链剂二胺单体,室温、氮气保护条件下充分反应后,经离心、过滤,得无色透明清液,置于有机溶液C 中沉淀,所述有机溶剂C为甲醇、乙醇、氯仿或二氯甲烷中的一种,得到白色粉状固体; After [0021] (2) The step (1) obtained was dissolved in an organic solution A, molar ratio, reaction well was added an excess of a diamine chain extender monomer, at room temperature, nitrogen blanket, by centrifugation, filtration , to give a transparent supernatant, the precipitate was placed in the organic solution C, the organic solvent C as a methanol, ethanol, chloroform or methylene chloride, to give a white powdery solid;

[0022] (3 )将步骤(2 )得到的产物溶解于有机溶液A中,再加入二异氰酸酯,按摩尔比,聚乙二醇:二异氰酸酯为1 : 1,在25 ~ 60 °C、氮气保护条件下反应; Obtained [0022] (3) Step (2) was dissolved in an organic solution A, was added a diisocyanate, a molar ratio of polyethylene glycol: diisocyanate is 1: 1, at 25 ~ 60 ° C, nitrogen the reaction conditions under protection;

[0023] (4)将步骤(3)得到的产物置于乙醚中沉淀,得到白色絮状固体,干燥后溶于氯仿中,倒入模具中成型,溶剂挥发晾干后,在蒸馏水中溶胀直至达到溶胀平衡,得到一种聚氨酯脲水凝胶。 After the obtained [0023] (4) The step (3) was placed the product precipitated with diethyl ether to give a white flocculent solid, after drying dissolved in chloroform, poured into a mold to solvent evaporation to dry, until the swelling in distilled water reached swelling equilibrium, to obtain a polyurethaneurea hydrogels.

[0024] 本发明技术方案中所述聚乙二醇的分子量为200~20000g/mol。 Aspect of the invention the molecular weight of the polyethylene glycol [0024] This is a 200 ~ 20000g / mol.

[0025]所述二异氰酸酯为脂肪链的二异氰酸酯0NC- (CH2) 4-NC0、0NC- (CH2) 6-NC0、 0NC- (CH2)s-NC0、0NC- (CH2) 12-NC0、1,5-二异氰酸-2-甲基戊烷中的一种,或为脂环族的二异氰酸酯)中'"monco [0025] The diisocyanate is aliphatic diisocyanate chain 0NC- (CH2) 4-NC0,0NC- (CH2) 6-NC0, 0NC- (CH2) s-NC0,0NC- (CH2) 12-NC0,1 , 5-diisocyanato-2-methylpentane of one, or from diisocyanates alicyclic) in ' "monco

Figure CN103524697BD00061

的一种,或为芳香族的二异氰酸酯 One, or from aromatic diisocyanate

Figure CN103524697BD00062

, ,

Figure CN103524697BD00063

a 中的一种。 One kind of a.

[0026]所述扩链剂二胺单体为 [0026] The chain extender is a diamine monomer

Figure CN103524697BD00064

、 、h2n- (ch2) 4-nh2、h2n- (ch2) 6-nh2、h2n- (ch2)s-nh2、h2n- (CH2) 1(]-νη2 中的一种。 ,, H2n- (ch2) 4-nh2, h2n- (ch2) 6-nh2, h2n- (ch2) s-nh2, h2n- (CH2) 1 (] - νη2 of one kind.

Figure CN103524697BD00065

[0027]所述扩链剂二胺单体为Hi [0027] The chain extender is a diamine monomer Hi

Figure CN103524697BD00066

,

Figure CN103524697BD00067

、H2N- (CH2) 4-NH2、H2N- (CH2) 6-NH2、H2N- (CH2)S-NH2、H2N- (CH2)i。 , H2N- (CH2) 4-NH2, H2N- (CH2) 6-NH2, H2N- (CH2) S-NH2, H2N- (CH2) i. -见12中的一种。 - See a medium 12.

[0028] 由于实施了上述技术方案,与现有技术相比,本发明优点在于: [0028] Since the embodiment of the above technical solution, compared with the prior art, advantages of the present invention comprising:

[0029] 1、由于合成的产物为线性分子,可溶于诸多有机溶剂或进行熔融加工,大大方便了其加工应用。 [0029] 1, since the linear molecules synthesized product is soluble in many organic solvent or melt processing, which greatly facilitates the processing of applications. 并且引入了大量的氨基甲酸酯基团及脲基,它们之间能够形成多重氢键,这种分子间的作用力能有效提供水凝胶的机械性能。 And the introduction of a large amount of urethane groups and urea groups, capable of forming multiple hydrogen bonding therebetween, the force between molecules effective to provide such mechanical properties of the hydrogel.

[0030] 2、在凝胶态时,脲基两边的疏水链自组装形成的疏水微区将氢键基团包裹起来, 将其与亲水聚合物链和凝胶网络中的水隔离开来,达到增强氢键的效果,这些增强了的氢键相互作用力又会使其外围的疏水外壳更加紧密聚集,实现氢键与疏水聚集作用力间的协同增强效应。 [0030] 2, when the gel state, both sides of the ureido hydrophobic chains form a hydrophobic self-assembled domains wrapped up the hydrogen-bonding groups, the hydrophilic polymer chains isolated from the gel network and open water , to enhance the effect of hydrogen bonds, which enhances the hydrogen bonding interaction will make the periphery of the hydrophobic shell gathering more closely to achieve a synergistic effect between hydrogen bonding and hydrophobic gathered force.

[0031] 3、本发明合成的聚氨酯脲水凝胶具有温度响应形状记忆功能的同时又具有室温下水响应形状记忆功能。 [0031] 3, the present invention is synthesized polyurethaneurea hydrogel while having a temperature responsive shape memory and having a water temperature responsive shape memory. 同时,还可依靠所制水凝胶的良好拉伸性能及PEG在脱水结晶-吸水去结晶过程中伴随的结晶相转变来实现室温、水介质条件下的形变产生、固定和恢复。 Meanwhile, also rely on good tensile properties and PEG hydrogel prepared in the dehydration crystallization - water absorption during crystallization to crystalline phase transition accompanied by deformation is achieved at room temperature, the aqueous medium condition occurs, the fixed and recovery.

附图说明 BRIEF DESCRIPTION

[0032] 图1是本发明实施例1提供的聚氨酯脲水凝胶的红外谱图; [0032] FIG. 1 is an infrared spectrum of Example 1 to provide polyurethaneurea hydrogel embodiment of the present invention;

[0033] 图2是本发明实施例1提供的聚氨酯脲水凝胶的核磁谱图; [0033] FIG. 2 is a NMR spectrum polyurethaneurea hydrogel according to one embodiment of the present invention is provided;

[0034] 图3是本发明实施例1提供的聚氨酯脲水凝胶的拉伸试验的应力-应变图; [0034] FIG. 3 is a tensile stress test polyurethaneurea hydrogel Example 1 of the present invention to provide - strain diagram;

[0035] 图4是本发明实施例1提供的聚氨酯脲水凝胶的300%下的五次循环拉伸试验的应力-应变图; [0035] FIG 4 is a cyclic tensile stress five test at 300% in Example 1 to provide polyurethaneurea hydrogels of the present invention - FIG strain;

[0036] 图5是本发明实施例1提供的聚氨酯脲水凝胶的200%下的五次循环拉伸试验的应力-应变图; [0036] FIG. 5 is a tensile stress test at five cycles of 200% in Example 1 to provide polyurethaneurea hydrogels of the present invention - FIG strain;

[0037] 图6是本发明实施例1提供的聚氨酯脲水凝胶的100%下的五次循环拉伸试验的应力-应变图; [0037] FIG. 6 is a tensile stress test of five cycles of 100% in Example 1 to provide polyurethaneurea hydrogels of the present invention - FIG strain;

[0038] 图7是本发明实施例1提供的使用分子量为4000g/mol的聚乙二醇合成的聚氨酯脲水凝胶的流变测试图; [0038] FIG. 7 is an embodiment used in Example 1 to provide a molecular weight of 4000g / mol polyethylene glycol polyurethaneurea hydrogels synthesized rheological test chart invention;

[0039] 图8是本发明实施例4提供的使用分子量为2000g/mol的聚乙二醇合成的聚氨酯脲水凝胶的流变测试图; [0039] FIG. 8 is a rheological tests provide a molecular weight for Example 4 2000g / mol synthetic polyethylene glycol polyurethaneurea hydrogels embodiment of the present invention;

[0040] 图9是本发明实施例4提供的聚氨酯脲水凝胶在不同含水量时的DSC测试曲线图。 [0040] FIG. 9 is a graph showing the DSC test of Example 4 provided polyurethaneurea hydrogels at different moisture contents embodiment of the present invention.

具体实施方式 Detailed ways

[0041] 下面结合附图和实施例对本发明技术方案作进一步的阐述。 Technical drawings and embodiments of the present invention will be further described [0041] below in conjunction.

[0042] 实施例1 [0042] Example 1

[0043] 本实施例提供的一种高强度聚氨酯脲水凝胶,其合成路线为: [0043] A high-strength polyurethaneurea hydrogel of the present embodiment is provided, which is a synthetic route:

[0044] [0044]

[0045] 式中,R代表二异氰酸酯中两个异氰酸根之间的烷基或芳香基,V代表二胺中两个胺基之间的烷基或芳香基,代表聚乙二醇(PEG),其分子量为200~20000g/ mol;n为聚合度。 [0045] In the formula, R represents between two isocyanate or two isocyanate-alkyl aryl, V Representative diamines between two aminoalkyl or an aryl group, representatives of polyethylene glycol (PEG ) having a molecular weight of 200 ~ 20000g / mol; n is the degree of polymerization.

[0046] 合成的具体步骤为:在分子量为4000g/mol的PEG的DMF溶液中加入二异氰酸酯0CN-(CH2)12-NC0,再加入5μL催化剂二月桂酸二丁基锡,80 °C下反应2h。 [0046] Synthesis of specific steps: the molecular weight of 4000g / DMF solution mol of PEG was added diisocyanate 0CN- (CH2) 12-NC0, then add 5μL catalyst dibutyl tin, 80 ° C for reaction 2h. 然后再向反应瓶中加入二胺氏~-(〇12)6-册1 2,在20°(:、氮气保护下搅拌反应3 11。严格控制反应原料的摩尔比,即PEG:二异氰酸酯:二胺=1 : 2 : 1。反应结束后将得到的黏度很大的溶液在正己烷中沉淀出来,得白色絮状固体。将产物进行干燥后溶到乙醇里,然后倒入模具中成型, 溶剂挥发晾干后,让其在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲的水凝胶。 To the reaction flask was then added to the diamine ~ s - (〇12) 6 volumes 12, the reaction was stirred at 20 ° (under nitrogen :, 3 molar ratio of 11. The strict control of the starting material, i.e. PEG: diisocyanate: diamines = 1: 2: 1. after the completion of reaction to give a large viscosity solution was precipitated out in n-hexane to give the product as a white flocculent solid was dried and dissolved in ethanol, and then poured into a mold to. after the solvent was evaporated dry, distilled water and allowed to swell until the swelling equilibrium, to obtain a polyurethaneurea hydrogel.

[0047] 参见附图1,它是本实施例提供的聚氨酯脲水凝胶的红外谱图;图中可见,2850 cm1:亚甲基峰;1670-1690cmS脲羰基;1530cmS氨基甲酸酯特征振动峰。 [0047] Referring to Figure 1, which is the present embodiment provides an infrared spectrum polyurethaneurea hydrogels embodiment; FIG seen, 2850 cm1: the methylene peaks; 1670-1690cmS urea groups; 1530cmS characteristic vibration carbamate peak.

[0048] 参见附图2,它是本实施例提供的聚氨酯脲水凝胶的核磁谱图;测试条件为0)(:13,11400/11-^^(400MHz,CDC13);其中δ= 7.26 (溶剂峰,CDC13) ;4.20 (氨基甲酸酯旁边碳上的氢);3· 79-3. 42 (4nH,PEG) ;3· 20-3. 10 (脲基旁边碳上的氢);1.90-1. 55 (氨基甲酸酯旁边碳上的氢);1· 40-1.20 (PEG)。 [0048] Referring to Figure 2, which is the NMR spectrum polyurethaneurea hydrogels according to this embodiment; test conditions 0) (: 13,11400 / 11 - ^^ (400MHz, CDC13); where δ = 7.26 (solvent peak, CDC13); 4.20 (hydrogens on the carbon next to carbamate);. 3 · 79-3 42 (4nH, PEG); (hydrogen on the carbon next ureido) 3 · 20-310.; . 1.90-1 55 (hydrogen on the carbon next to carbamate); 1 · 40-1.20 (PEG).

[0049] 本实施例用脂肪链的二异氰酸酯和二胺合成线型的大分子聚氨酯脲水凝胶,具有如下结构: [0049] The diisocyanate and the diamine of Example synthesizing a linear aliphatic chain with the present embodiment macromolecules polyurethaneurea hydrogel, having the following structure:

[0050] [0050]

Figure CN103524697BD00081

[0051] 式中,R代表二异氰酸酯中两个异氰酸根之间的烷基或芳香基,R'代表二胺中两个胺基之间的烷基或芳香基,^代表聚乙二醇(PEG),其分子量为200~20000g/ mol;n为聚合度。 [0051] In the formula, R represents between two isocyanate or two isocyanate-alkyl aryl group, R 'an alkyl group or an aromatic diamine behalf between two amine groups, polyethylene glycol Representative ^ (PEG), having a molecular weight of 200 ~ 20000g / mol; n is the degree of polymerization. 这种线性的长链分子中含有大量的脲基,脲基之间会形成大量的氢键,同时分子中的疏水链自组装形成的疏水微区将氢键基团包裹起来,将其与亲水聚合物链和凝胶网络中的水隔离开来,达到增强氢键的效果,这些增强了的氢键相互作用力又会使其外围的疏水外壳更加紧密聚集,实现氢键与疏水聚集作用力间的协同增强效应,因此,机械性得到了有效的改善。 This linear molecule contains a large number of long chain ureido group, a large number of hydrogen bonds formed between urea groups, while the hydrophobic chains in the molecule a hydrophobic self-assembling micro domains formed of hydrogen-bonding groups will be wrapped up, and its parent isolated from water and water of polymer chains in the gel network open to achieve the effect of enhancing hydrogen bonding, which enhance the hydrogen bonding interaction force will make the periphery of the housing hydrophobic aggregates more closely, and achieve hydrogen bonding hydrophobic aggregation synergistic effect between the force, and therefore, mechanical been effectively improved.

[0052] 参见附图3,它是本实施例提供的聚氨酯脲水凝胶的拉伸测试曲线图,由图中可以看出,其断裂伸长率为1320 %,对应的应力为2000kPa。 [0052] Referring to Figure 3, which is a graph of tensile testing of the present polyurethaneurea hydrogel according to an embodiment, it can be seen from the figure, the elongation at break was 1320%, the corresponding stress of 2000kPa. 也就是,这种水凝胶可以拉到原长的13倍左右才会发生断裂,并且最高承受的拉伸力为2000kPa。 That is, such hydrogels can be pulled about 13 times the original length before fracture occurs, and is subjected to the highest tensile force to 2000kPa. 本发明合成的产物其断裂伸长率的范围可以在200 % ~ 2000 %内进行调节,这种高强度的性质有可能应用于组织工程支架以及软骨的替换等生物材料。 Range of the elongation at break of the present invention, the synthesized product can be adjusted within a 200% to 2000% of this nature is likely to be applied to high-strength tissue engineering scaffold and the cartilage replacement other biological materials.

[0053] 参见附图4,它是本实施例提供的聚氨酯脲水凝胶的循环拉伸测试曲线图,图4、 图5、图6分别为300 %、200 %、100 %下的五次循环拉伸测试。 [0053] Referring to Figure 4, which are cyclic polyurethaneurea hydrogels according to an embodiment of a tensile test graph, FIG. 4, FIG. 5, FIG. 6 is 300%, 200% and 100% of the five cyclic tensile testing. 由图可见,300 %,200 %循环拉伸测试在第一个循环的过程中,样品都发生了一定程度的能量损耗,当应力为零时,横坐标对应的应变分别为20 %和12 %,也就是在一个循环拉伸后,样品分别能回复到原长的80 %和88 %。 Seen from the FIG., 300%, 200% tensile testing cycle during a first cycle, the samples have undergone some degree of energy loss, when the stress is zero, the abscissa corresponding to a strain of 20% and 12%, respectively , i.e. one cycle after stretching, the sample can reply to respectively 80% and 88% of the original length. 随后的四次循环在同样的应变下都不能回复到原来的应力的位置,但是随后的四次循环其应力-应变曲线基本上差别不大。 Followed by four cycles in the same strain can not return to the original position of the stress, but the subsequent four cycles stress - strain curve is substantially not very different. 不同于以上两种曲线,100 %的循环拉伸过程中,其回复性比较好,没有出现能量耗散圈。 Different for the two curves, 100% stretching process cycle, which is better recovery, no energy dissipation ring. 由此可以看出,该聚氨酯脲水凝胶在多次拉伸时会发生一定程度的能量耗散,使其不能回复到原长,但是这种耗散不是很大,说明样品有很好的弹性,尤其是当拉伸程度不是很大时,样品基本能回复到原长。 It can be seen, the polyurethaneurea hydrogel certain degree of energy dissipation occurs when multiple stretching, it can not return to its original length, but this is not dissipative large then the sample is good elasticity, when the degree of stretching is not particularly large, the sample can be returned to substantially its original length.

[0054] 参见附图7,它是本实施例提供的聚氨酯脲水凝胶的流变测试图;横坐标是角速度,纵坐标为应力,两条线分别为弹性模量和黏性模量随角速度变化的曲线。 [0054] Referring to Figure 7, which is FIG rheological tests polyurethaneurea hydrogel according to this embodiment; the abscissa is the angular velocity, the ordinate is the stress, the two lines are the elastic modulus and the viscous modulus with angular speed variation curve. 图7是使用分子量为4000g/mol的聚乙二醇合成的聚氨酯脲水凝胶的流变图。 FIG 7 is a molecular weight of 4000g / mol polyethylene glycol polyurethaneurea hydrogels synthesized rheological FIG. 从图中可以看出,G'弹性模量曲线始终处于G"黏性模量曲线的上方,说明这种水凝胶表现出了固体的性质,而且其弹性模量约为45kPa,也反映了水凝胶的强度比较好。 As can be seen from the figure, G 'is the elastic modulus curve is always above G "the viscous modulus curve, indicating that such hydrogels exhibit properties of a solid, and the elastic modulus of about 45kPa, also reflects strength of the hydrogel is better.

[0055] 本实施例提供的聚氨酯脲水凝胶具有水和热响应形状记忆功能。 [0055] The polyurethaneurea hydrogel of the present embodiment provided with the water and thermally responsive shape memory.

[0056] 水响应的形状记忆条件是:将聚氨酯脲水凝胶溶胀后设计成初始形状,在其溶胀后利用其高弹性在室温下的拉伸-脱水后得到临时形状,将固定后的临时形状的干态凝胶放入室温下的蒸馏水中吸水后,其形状恢复到初始形状,实现形状的记忆功能。 [0056] Shape memory condition in response to the water are: polyurethane urea designed to original shape after swelling of the hydrogel, with its high elasticity after stretching swell at room temperature - temporary shape obtained after dehydration, after the temporary fixing after the dry gel shaped into distilled water at room temperature water absorption, shape recovery to the original shape, the shape memory to achieve.

[0057] 热响应的形状记忆条件是:将聚氨酯脲水凝胶溶胀后设计成初始形状,将聚氨酯脲水凝胶加热到50 °C后对其进行拉伸得到临时形状,将固定后的临时形状的干态凝胶放入50 °C硅油中,其形状恢复到初始形状,实现形状的记忆功能。 [0057] The thermally responsive shape memory condition is: the design polyurethaneurea hydrogels swell to the original shape, the polyurethaneurea hydrogel was heated to 50 ° C may be stretched to obtain a temporary shape, the temporary fixing after the dry gel was put in the shape of 50 ° C in a silicone oil, which is restored to the original shape of a shape, the shape memory to achieve.

[0058] 实施例2 [0058] Example 2

[0059] 本实施例提供一种高强度聚氨酯脲水凝胶的合成方法,具体步骤如下: [0059] The embodiment provides a high-strength polyurethaneurea hydrogels synthesis method of the present embodiment, the following steps:

[0060] 在分子量为10000g/mol的PEG丙酮溶液中加入二异氰酸酯IPDI,再加入5μ1 催化剂辛酸亚锡,50 °C下反应3h。 PEG acetone [0060] molecular weight of 10000g / mol was added diisocyanate IPDI, the reaction was added at 3h 5μ1 stannous octoate catalyst, 50 ° C. 然后再向反应瓶中加入二胺3, 3'-甲撑二苯胺,40 °C下氮气保护搅拌反应3h。 To the reaction flask was then added to the diamine 3,3'-methylene dianiline, nitrogen The reaction was stirred 40 ° C for 3h. 严格控制反应原料的摩尔比,即PEG:二异氰酸酯:二胺= 1 : 2 : 1。 Molar ratio of strict control of the starting material, i.e. PEG: diisocyanate: diamine = 1: 2: 1. 反应结束后将得到的黏度很大的溶液在乙醚中沉淀出来,得白色絮状固体。 After completion of the reaction the obtained solution viscosity greatly precipitated in ether to give a white flocculent solid. 将产物进行干燥后溶到氯仿里,然后倒入模具中成型,溶剂挥发晾干后,让其在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲的水凝胶。 The product was dissolved in chloroform and dried, and then poured into a mold to dry after evaporation of the solvent, allowed to swell in distilled water until the swelling equilibrium, to obtain a polyurethaneurea hydrogel.

[0061] 本实施例的特点是使用脂环族的二异氰酸酯IPDI与分子量为6000g/mol的PEG 反应,然后再与带苯环的芳香族二胺合成聚氨酯脲水凝胶。 [0061] Characteristics of the present embodiment is the use of a diisocyanate with a molecular weight of IPDI cycloaliphatic was 6000g / PEG mol of the reaction, and then with an aromatic diamine to phenyl urea synthesis of the polyurethane hydrogel.

[0062] 实施例3 [0062] Example 3

[0063] 本实施例提供的高强度聚氨酯脲水凝胶。 [0063] The present embodiment provides a high strength polyurethane urea hydrogel. 其合成方法的具体步骤如下: The specific step of the synthesis method are as follows:

[0064] 在分子量为200g/mol的PEG丙酮溶液中加入二异氰酸酯1,3-二异苯氰酸酯,再加入5μL催化剂吡啶,80Γ下反应3h。 [0064] The molecular weight of PEG in acetone 200g / mol was added 1,3-diisocyanate, phenylene diisocyanate, diisocyanate, then add 5μL pyridine catalyst, the reaction 80Γ 3h. 然后再向反应瓶中加入二胺°C下氮气保护搅拌反应3h。 To the reaction flask was then added under nitrogen diamine ° C the reaction was stirred 3h. 严格控制反应原料的摩尔比,即PEG:二异氰酸酯:二胺= 1 : 2 : 1。 Molar ratio of strict control of the starting material, i.e. PEG: diisocyanate: diamine = 1: 2: 1. 反应结束后将得到的黏度很大的溶液在正己烷中沉淀出来,得白色絮状固体。 After completion of the reaction the obtained solution viscosity greatly precipitated in n-hexane to give a white flocculent solid. 将产物进行干燥后溶到甲醇里,然后倒入模具中成型,溶剂挥发晾干后,让其在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲的水凝胶。 The product was dissolved into methanol and dried, and then poured into a mold to dry after evaporation of the solvent, allowed to swell in distilled water until the swelling equilibrium, to obtain a polyurethaneurea hydrogel.

[0065] 本实施例的特点是使用芳香族的二异氰酸酯与低分子量的PEG反应,然后再与脂肪族带侧基的二胺反应合成聚氨酯脲水凝胶。 [0065] Characteristics of the present embodiment is a PEG reaction using an aromatic diisocyanate with a low molecular weight, and then with an aliphatic diamine with side groups were synthesized polyurethaneurea hydrogels.

[0066]实施例4 [0066] Example 4

[0067] 本实施例提供的一种高强度聚氨酯脲水凝胶,合成路线如下: [0067] A high-strength present polyurethaneurea hydrogels, synthetic routes provided by the embodiment is as follows:

[0068] [0068]

Figure CN103524697BD00101

,

[0069] 式中,R代表二异氰酸酯中两个异氰酸根之间的烷基或芳香基,V代表二胺中两个胺基之间的烷基或芳香基,^代表聚乙二醇(PEG),其分子量为200~20000g/ mol;n为聚合度。 [0069] In the formula, R represents between two isocyanate or two isocyanate-alkyl aryl, V between two representatives of diamines alkyl or aryl amine, ^ Representative polyethylene glycol ( PEG), having a molecular weight of 200 ~ 20000g / mol; n is the degree of polymerization.

[0070] 合成的具体步骤为: [0070] Synthesis of specific steps:

[0071] 第一步,在分子量为2000g/mol的PEG的有机溶液中加入N,f-二羰基二咪唑, 室温下氮气保护,搅拌反应30h,反应结束后将溶液在乙醚里沉淀,得白色粉状沉淀,抽滤掉乙醚后,将产物干燥。 [0071] The first step, adding a molecular weight 2000g / mol of PEG organic solution N, f- dicarbonyl diimidazole, nitrogen at room temperature, the reaction was stirred for 30h, after completion of the reaction solution was precipitated in diethyl ether to give a white powdery precipitate was suction filtered with ether, the product was dried.

[0072] 第二步,将第一步得到的产物用氯仿溶解后,加入H2N_(CH2) 12-NH2,使最初反应的聚乙二醇:H2N-(CH2)12-NH2=1 : 16 (摩尔比)。 [0072] The second step, after the first step obtained product was dissolved in chloroform, was added H2N_ (CH2) 12-NH2, so that the initial reaction of polyethylene glycol: H2N- (CH2) 12-NH2 = 1: 16 ( The molar ratio of). 氮气保护下,室温反应72h,得到两端是胺基的大分子,将产物离心后用硅藻土过滤掉上层固体得无色透明清液,将得到的清液在乙醚里沉淀,得白色粉状固体二胺。 Under nitrogen at rt for 72h, to give an amine ends are macromolecules, the product was centrifuged and filtered off through celite to give a colorless transparent solid upper supernatant and the resulting clear solution was precipitated in diethyl ether, as a white powder solid diamine.

[0073] 第三步,向第二步合成的二胺中加入0CN-(CH2)6-NC0,使最初反应的聚乙二醇:二异氰酸酯=1 : 1 (摩尔比),在50 °C下氮气保护搅拌反应5h。 [0073] The third step, the second step of the synthesis of the diamine was added 0CN- (CH2) 6-NC0, so that the initial reaction of polyethylene glycol: diisocyanate = 1: 1 (molar ratio), 50 ° C and the reaction was stirred under nitrogen for 5h. 反应结束后将得到的黏度很大的溶液在乙醚里沉淀出来,得白色絮状固体。 After the reaction solution obtained great viscosity was precipitated in ether to give a white flocculent solid. 将产物进行干燥后溶到氯仿里,然后倒入模具中成型,溶剂挥发晾干后,让其在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲的水凝胶。 The product was dissolved in chloroform and dried, and then poured into a mold to dry after evaporation of the solvent, allowed to swell in distilled water until the swelling equilibrium, to obtain a polyurethaneurea hydrogel.

[0074] 本实施例的特点在是先合成大分子的胺,利用分子量为4000g/mol的PEG与脂肪链的二胺H2N- (CH2) 12-NH2,再与脂肪链的二异氰酸酯反应,最后得到线型的大分子聚氨酯脲。 [0074] Features of the present embodiment is the first embodiment of the amine synthesized macromolecules by molecular weight of 4000g / mol of PEG chains with the aliphatic diamine H2N- (CH2) 12-NH2, and then with a diisocyanate chain fatty ester, and finally linear macromolecules obtained polyurethane urea.

[0075] 参见附图8,图8是本实施例中使用分子量为2000g/mol的聚乙二醇合成的聚氨酯脲水凝胶的流变图。 [0075] 8 Referring to the drawings, FIG. 8 is a polyurethaneurea hydrogel embodiments a molecular weight of 2000g / mol in the present embodiment the synthesis of polyethylene glycol rheological FIG. 图中,G'弹性模量曲线也是处于G"黏性模量曲线的上方,并且对应的弹性模量约为50kPa,说明此路线合成的聚氨酯脲的水凝胶与使用小分子胺扩链剂路线合成的水凝胶的强度在一个数量级上,证明本发明提供的两种合成的聚氨酯脲水凝胶的方法都可以达到很好的机械性能。 FIG, G 'is the elastic modulus curve is above G "the viscous modulus curve, and the corresponding elastic modulus of about 50 kPa, the description of this synthetic route polyurethaneurea hydrogel small molecule chain extender amine strength synthetic route hydrogel in an order of magnitude, the present invention provides two kinds of proof synthetic methods polyurethaneurea hydrogels can achieve very good mechanical properties.

[0076] 参见附图9,它是本实施例提供的聚氨酯脲水凝胶在不同含水量时所测得的DSC 曲线图。 [0076] Referring to FIG. 9, which is a graph of DSC present polyurethaneurea hydrogels provided at different moisture contents measured embodiments. 从图中可看出,随着含水量的增加,结晶区的熔点逐渐降低。 As can be seen from the figure, as the water content increases, the melting point of the crystalline region gradually decreases. 这就是聚氨酯脲水凝胶能够具有水响应形状记忆功能的原因,即依靠外界的水来改变结晶区的转变温度,从而能在一定的含水量以上达到恢复最初原始形状的功能。 This is polyurethaneurea hydrogels can be reasons for having shape memory in response to water, i.e., water to rely on external transition temperature in the crystallization zone change, so that it can restore the original reaches the original shape function above a certain moisture content.

[0077] 实施例5 [0077] Example 5

[0078] 本实施例提供的一种高强度的聚氨酯脲水凝胶的合成方法,具体步骤如下: [0078] The synthetic method provided polyurethaneurea hydrogel a high strength of the present embodiment, the following steps:

[0079] 在分子量为20000g/mol的PEG的DMF中加入N,N'-二羰基二咪唑,室温、氮气保护下,搅拌反应30h,反应结束后将溶液在正庚烷里沉淀,抽滤掉溶剂后,将产物干燥。 [0079] Add a molecular weight of 20000g / mol of PEG of DMF of N, N'- dicarbonyl diimidazole, at room temperature, nitrogen atmosphere, the reaction was stirred for 30h, after completion of the reaction solution was precipitated in n-heptane, filtered off with suction after the solvent, the product was dried. 然后将第一步的产物用氯仿溶解后,加入1,4-二氨基环己烷,使最初反应的聚乙二醇:1,4-二氨基环己烷=1 : 16 (摩尔比)。 After the first step the product was then dissolved in chloroform, 1,4-diaminocyclohexane, so that the initial reaction of polyethylene glycol: 1,4-diaminocyclohexane = 1: 16 (molar ratio). 氮气保护下,室温反应72h,得到两端是胺基的大分子,将产物离心后用硅藻土过滤掉上层固体得无色透明清液,将得到的清液在乙醚里沉淀,得白色粉状固体。 Under nitrogen at rt for 72h, to give an amine ends are macromolecules, the product was centrifuged and filtered off through celite to give a colorless transparent solid upper supernatant and the resulting clear solution was precipitated in diethyl ether, as a white powder solid. 第三步是向第二步合成的二胺中加入1,3-二异苯氰酸酯,使最初反应的聚乙二醇:二异氰酸酯=1 : 1 (摩尔比),在60 °C下氮气保护搅拌反应3h。 The third step is the second step of the synthesis of 1,3-di-diamine phenyl diisocyanate, so that the initial reaction of polyethylene glycol: diisocyanate = 1: 1 (molar ratio), at 60 ° C under The reaction was stirred for 3h nitrogen. 反应结束后将得到的黏度很大的溶液在乙醚里沉淀出来,得白色絮状固体。 After the reaction solution obtained great viscosity was precipitated in ether to give a white flocculent solid. 将产物进行干燥后溶到氯仿里, 然后倒入模具中成型,溶剂挥发晾干后,让其在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲的水凝胶。 The product was dissolved in chloroform and dried, and then poured into a mold to dry after evaporation of the solvent, allowed to swell in distilled water until the swelling equilibrium, to obtain a polyurethaneurea hydrogel.

[0080] 本实施例的特点是先利用PEG与环状的二胺合成大分子的两端带胺基的大分子, 然后让其再与芳香族的二异氰酸酯反应,从而合成最终的聚氨酯脲水凝胶。 Characteristics ends macromolecules [0080] to the present embodiment is a PEG diamine with a cyclic amine with a synthetic macromolecule, and then allowed to react with an ester of an aromatic diisocyanate, to synthesize the final polyurethane urea water gel.

Claims (8)

1. 一种制备聚氨醋脈水凝胶的方法,其特征在于包括如下步骤: (1) 将聚乙二醇溶解于有机溶液A中,所述有机溶剂A为DMF、丙酬、氯仿、二氯甲烧、 二氯乙烧中的一种;再加入二异氯酸醋和催化剂,所述催化剂为辛酸亚锡、二月桂酸二下基锡、N-乙基吗嘟、N-甲基吗嘟、化晚、N,N'-二甲基化晚中的一种;在溫度为20 ~ 80°C 的条件下反应1 ~ 5小时,按摩尔比,聚乙二醇:二异氯酸醋为1 : 2 ; (2) 加入扩链剂二胺单体,在溫度为20 ~ 80 °C,氮气保护下揽拌反应1 ~ 5小时,按摩尔比,聚乙二醇:二异氯酸醋:二胺为1 : 2 : 1 ; (3) 反应结束后将产物置于有机溶剂B中,所述有机溶剂B为正己烧、正庚烧、异己烧、 异庚烧、环己烧、乙酸中的一种,得到白色絮状固体沉淀物;干燥后再溶解于有机溶剂C中, 所述有机溶剂C为甲醇、乙醇、氯仿或二氯甲烧中的一种,倒入模 1. A method of preparing polyurethane hydrogel pulse of vinegar, comprising the steps of: (1) Polyethylene glycol dissolved in an organic solution A, A is the organic solvent of DMF, propyl paid, chloroform, dichloromethane burning a burning in dichloroacetyl; vinegar was added diisopropyl acid catalyst and the catalyst is stannous octoate, dibutyltin dilaurate under, N- ethylmorpholine beep, N- methyl group it beep, of late, N, N'-dimethylated of one night; for 1 to 5 hours at a temperature of 20 ~ 80 ° C conditions, the molar ratio of polyethylene glycol: diisopropyl acid vinegar, 1: 2; (2) a chain extender diamine monomer is added at a temperature of 20 ~ 80 ° C, the reaction mix embrace 1 to 5 hours under nitrogen, a molar ratio of polyethylene glycol: two acid isopropyl acetate: diamine is 1: 2: 1; end (3) after the reaction product was placed in an organic solvent B in the organic solvent is n-hexyl B burn, burn n-heptyl, isohexyl, burn, burn isoheptyl, ring hexyl burning an acetic acid, to give a white flocculent solid precipitate; dry and then dissolved in an organic solvent C in the organic solvent C is one of methanol, ethanol, chloroform or dichloromethane in the burning, poured mold 具中成型,溶剂挥发惊干后,在蒸馈水中溶胀直至达到溶胀平衡,得到一种聚氨醋脈水凝胶。 With molded, shock dry solvent evaporation, the steam feed swells in water until swelling equilibrium, to obtain a polyurethane hydrogel pulse vinegar.
2. 根据权利要求1所述的一种制备聚氨醋脈水凝胶的方法,其特征在于:所述聚乙二醇的分子量为200~20000g/mol。 The method for preparing a polyurethane hydrogel pulse vinegar according to claim 1, wherein: said polyethylene glycol has a molecular weight of 200 ~ 20000g / mol.
3. 根据权利要求1所述的一种制备聚氨醋脈水凝胶的方法,其特征在于:所述二异氯酸醋为脂肪链的二异氯酸醋ONC-(邸2) 4-NC0、ONC-(邸2)e-NCO、ONC-(邸2)S-NCO、 0NC-(CH2)i2-NC0、1,5-二异氯酸-2-甲基戊烧中的一种,或为脂环族的二异氯酸醋 The method for preparing a polyurethane hydrogel pulse vinegar according to claim 1, wherein: said acid diisopropyl diisobutyl ONC- vinegar vinegar acid fatty chain (Di 2) ​​4- NC0, ONC- (Di 2) ​​e-NCO, ONC- (Di 2) ​​S-NCO, 0NC- one kind (CH2) i2-NC0,1,5- acid diisopropyl methylpentyl Sinter acid diisopropyl vinegar, alicyclic group or
Figure CN103524697BC00021
中的一种,或为芳香族的二异氯酸醋 Of one, or aromatic di-acid of vinegar
Figure CN103524697BC00022
Figure CN103524697BC00023
4. 根据权利要求1所述的一种制备聚氨醋脈水凝胶的方法,其特征在于: 所述扩链剂二胺单体为 The method of preparing a polyurethane hydrogel pulse vinegar according to claim 1, wherein: the chain extender is a diamine monomer
Figure CN103524697BC00024
、HzN-(邸2)广畑2、HzN-(邸2)(;-畑2、HzN-(邸2)广畑2、HzN-(邸2) 1广畑2 中的一种。 , HzN- (Di 2) ​​2 Hirohata, HzN- (Di 2) ​​(; - Hata 2, HzN- (Di 2) ​​2 Hirohata, HzN- (Di 2) ​​A 1 2 Hirohata.
5. -种制备聚氨醋脈水凝胶的方法,其特征在于包括如下步骤: (1) 将聚乙二醇溶解于有机溶液A中,所述有机溶剂A为DMF、丙酬、氯仿、二氯甲烧、二氯乙烧中的一种;按摩尔比,再加入过量的N,N'-幾基二咪挫,室溫、氮气保护条件下充分反应,结束后将溶液在有机溶剂B中沉淀,所述有机溶剂B为正己烧、正庚烧、异己烧、异庚烧、环己烧、乙酸中的一种;将得到的白色粉状沉淀物抽滤、干燥; (2) 将步骤(1)得到的产物溶解在有机溶液A中,按摩尔比,加入过量的扩链剂二胺单体,室溫、氮气保护条件下充分反应后,经离屯、、过滤,得无色透明清液,置于有机溶液C中沉淀,所述有机溶剂C为甲醇、乙醇、氯仿或二氯甲烧中的一种,得到白色粉状固体; (3) 将步骤(2)得到的产物溶解于有机溶液A中,再加入二异氯酸醋,按摩尔比,聚乙二醇:二异氯酸 5. - The method of preparing polyurethane hydrogel pulse vinegar species, characterized by comprising the steps of: (1) Polyethylene glycol dissolved in an organic solution A, A is the organic solvent of DMF, propyl paid, chloroform, dichloromethane burning a burning in dichloroacetyl; molar ratio, then adding an excess of N, N'- sufficient reaction under several diamidino-yl setback, room temperature, nitrogen blanket, a solution in an organic solvent after the end of B precipitated, the organic solvent is n-hexyl B burn, burn n-heptyl, isohexyl, burn, burn iso-heptyl, cyclohexyl burning an acetic acid; the resulting white powdery precipitate was filtered off with suction and dried; (2) after step (1) obtained was dissolved in an organic solution a, molar ratio, reaction well was added an excess of a diamine chain extender monomer, at room temperature, nitrogen blanket, dried Tun ,, filtered off to give no colorless transparent supernatant, the precipitate was placed in the organic solution C, the organic solvent C is one of methanol, ethanol, chloroform or dichloromethane in the burning, to give a white powdery solid; (2) to give (3) the step A product was dissolved in the organic solution, the vinegar was added diisopropyl acid, molar ratio of polyethylene glycol: di-acid 为1 : 1,在25 ~ 60 °C、氮气保护条件下反应; (4) 将步骤(3)得到的产物置于乙酸中沉淀,得到白色絮状固体,干燥后溶于氯仿中,倒入模具中成型,溶剂挥发惊干后,在蒸馈水中溶胀直至达到溶胀平衡,得到一种聚氨醋脈水凝胶。 1: 1, at 25 ~ 60 ° C, a nitrogen blanket the reactor; obtained in (4) of step (3) of the product precipitated in acetic acid, to give a white flocculent solid, after drying dissolved in chloroform, poured into a mold forming, solvent evaporation shock dryness, distilled water until the feed reached swelling equilibrium swelling, to give a polyurethane hydrogel pulse vinegar.
6. 根据权利要求5所述的一种制备聚氨醋脈水凝胶的方法,其特征在于:所述聚乙二醇的分子量为200~20000g/mol。 A method for preparing a polyurethane hydrogel pulse vinegar according to claim 5, wherein: said polyethylene glycol has a molecular weight of 200 ~ 20000g / mol.
7. 根据权利要求5所述的一种制备聚氨醋脈水凝胶的方法,其特征在于:所述二异氯酸醋为脂肪链的二异氯酸醋ONC-(邸2) 4-NC0、ONC-(邸2)e-NCO、ONC-(邸2)S-NCO、 0NC-(CH2)i2-NC0、1,5-二异氯酸-2-甲基戊烧中的一种,或为脂环族的二异氯酸醋 A method for preparing a polyurethane hydrogel pulse vinegar according to claim 5, wherein: said acid diisopropyl diisobutyl ONC- vinegar vinegar acid fatty chain (Di 2) ​​4- NC0, ONC- (Di 2) ​​e-NCO, ONC- (Di 2) ​​S-NCO, 0NC- one kind (CH2) i2-NC0,1,5- acid diisopropyl methylpentyl Sinter acid diisopropyl vinegar, alicyclic group or
Figure CN103524697BC00031
8. 根据权利要求5所述的一种制备聚氨醋脈水凝胶的方法,其特征在于:所述扩链剂二胺单体为跑 A method for preparing a polyurethane hydrogel pulse vinegar according to claim 5, wherein: the chain extender is a diamine monomer run
Figure CN103524697BC00032
.踢张~f游、i泌乃與~勺邮、 HzN-畑2) 4_畑2、脚-畑2) 6_畑2、HzN-畑2) 8_畑2、脚-畑2) 1〇-畑2中的一种。 . ~ F kicked Zhang tour, i ~ and secretion is the spoon-mail, HzN- Hata 2) 4_ Hata 2 feet - Hata 2) 6_ Hata 2, HzN- Hata 2) 8_ Hata 2 feet - Hata 2) 2 of one 1〇- Hata.
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CN105237714A (en) * 2014-07-08 2016-01-13 理大产学研基地(深圳)有限公司 Water response shape memory polyurethane and preparation method therefor
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CN105801809B (en) * 2016-05-04 2018-08-03 湖南科技大学 The method of producing a double-sensitive polyurethane hydrogels
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CN106046311B (en) * 2016-07-05 2018-06-22 湖南科技大学 Amphoteric ionic smart responsive hydrogels prepared
CN106008914B (en) * 2016-07-05 2018-06-22 湖南科技大学 Preparation methods in response to the dual hydrogel both acid sensitive groups
CN105906782B (en) * 2016-07-05 2018-04-03 湖南科技大学 Preparing a polyurethane having a pH amphoteric hydrogel group response
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5000955A (en) * 1988-07-29 1991-03-19 Tyndale Plains-Hunter Ltd. Thermally reversible polyurethane hydrogels and cosmetic, biological and medical uses
US5662960A (en) * 1995-02-01 1997-09-02 Schneider (Usa) Inc. Process for producing slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with a poly (n-vinylpyrrolidone) polymer hydrogel
JP2001040057A (en) * 1999-05-24 2001-02-13 Toyo Ink Mfg Co Ltd Production of polyurethane-polyurea, and use of polyurethane-polyurea obtained thereby
CN102604032A (en) * 2012-02-28 2012-07-25 华南理工大学 Thermo-sensitive chain extender and polyurethane hydrogel with double sensitivity of temperature and pH
CN102875772A (en) * 2012-10-19 2013-01-16 中国科学院长春应用化学研究所 Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5000955A (en) * 1988-07-29 1991-03-19 Tyndale Plains-Hunter Ltd. Thermally reversible polyurethane hydrogels and cosmetic, biological and medical uses
US5662960A (en) * 1995-02-01 1997-09-02 Schneider (Usa) Inc. Process for producing slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with a poly (n-vinylpyrrolidone) polymer hydrogel
JP2001040057A (en) * 1999-05-24 2001-02-13 Toyo Ink Mfg Co Ltd Production of polyurethane-polyurea, and use of polyurethane-polyurea obtained thereby
CN102604032A (en) * 2012-02-28 2012-07-25 华南理工大学 Thermo-sensitive chain extender and polyurethane hydrogel with double sensitivity of temperature and pH
CN102875772A (en) * 2012-10-19 2013-01-16 中国科学院长春应用化学研究所 Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel

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