WO2016086585A1 - 一种两性离子型形状记忆聚氨酯及其制备方法 - Google Patents

一种两性离子型形状记忆聚氨酯及其制备方法 Download PDF

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WO2016086585A1
WO2016086585A1 PCT/CN2015/078027 CN2015078027W WO2016086585A1 WO 2016086585 A1 WO2016086585 A1 WO 2016086585A1 CN 2015078027 W CN2015078027 W CN 2015078027W WO 2016086585 A1 WO2016086585 A1 WO 2016086585A1
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monomer
shape memory
zwitterionic
polyurethane
memory polyurethane
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French (fr)
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陈少军
杨艳
莫富年
任换换
戈早川
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深圳大学
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C—CHEMISTRY; METALLURGY
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

  • the invention relates to the field of polymer materials, in particular to a zwitterionic shape memory polyurethane and a preparation method thereof.
  • Shape memory effect refers to the ability to sense environmental changes (such as temperature, force, electromagnetic, solvent, etc.), can be deformed and fixed to obtain a temporary shape; and after sensing changes in the external environment, it can change the shape back to the original shape.
  • shape memory materials can be divided into shape-memory materials such as heat-sensitive, photo-sensitive, electro-sensitive and chemical-sensitive.
  • shape-memory materials such as heat-sensitive, photo-sensitive, electro-sensitive and chemical-sensitive.
  • polymer shape memory materials are widely used in textile, medical, aerospace, engineering and other fields.
  • researchers at home and abroad have developed and applied a variety of thermotropic shape memory polymers using chemical and physical methods. However, the general comprehensive performance is not ideal.
  • thermotropic shape memory polymer is to meet the clinical application of biomedicine, it needs to have mild stimulation conditions close to human body temperature or biological environment, and moderate biocompatibility and suitable strength. And other comprehensive performance. Therefore, the development of thermal-induced shape memory polymers with low cost, simple processing, multiple properties and good biocompatibility is the development direction of current theoretical and applied research.
  • zwitterionic polymer As a kind of polymer material, zwitterionic polymer has unique properties and has attracted worldwide attention in recent years. When the polymer chain contains both anionic and cationic groups, it is called a zwitterionic polymer, which is a relatively unique polyelectrolyte. Zwitterionic polymers have been widely used in biomedical materials because of their good chemical properties, hydration ability, and are not easily affected by solution values, which has led to rapid development of life sciences.
  • a betaine-type zwitterionic polymer refers to a type of polymer having a structure similar to the natural product betaine structure and having a cation and an anion in the same monomer structure. Betaine-type zwitterionic polymers are hydrated due to their chemical and thermal stability.
  • the present invention provides a zwitterionic shape memory polyurethane and a preparation method thereof, and a zwitterionic shape memory polyurethane based on an N-alkyldialkylolamine having shape memory properties and good biological properties. Compatibility, aimed at solving the problem of poor biocompatibility of existing shape memory polymers.
  • a method for preparing a zwitterionic shape memory polyurethane comprising the steps of:
  • Step 1 synthesizing the N-alkyldialkylolamine-based polyurethane from the monomers A and B by a polymerization method, or by a stepwise polymerization method from the monomers A, B and C;
  • Step 2 synthesizing the zwitterionic shape memory polyurethane by ring-opening reaction of monomer D on the N group of the N-alkyl dialkylolamine-based polyurethane;
  • the monomer A is an N-alkyl dialkyl alcohol amine, and its chemical structural formula is as follows:
  • Monomer B is a polyisocyanate
  • monomer C is a polyhydric alcohol
  • monomer D is an alkyl sultone.
  • step one The preparation method of the zwitterionic shape memory polyurethane, wherein the specific process of step one is as follows:
  • the method for preparing a zwitterionic shape memory polyurethane wherein the second step further comprises the following steps:
  • the zwitterionic shape memory polyurethane solution is volatilized in an organic solvent at 80 to 100 °C.
  • the method for preparing a zwitterionic shape memory polyurethane wherein the zwitterionic shape memory polyurethane solution is sequentially subjected to a blast oven and a vacuum drying oven at 80 to 100 ° C to volatilize an organic solvent.
  • the method for preparing a zwitterionic shape memory polyurethane wherein the organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide or tetrahydrofuran;
  • Monomer B is an aliphatic polyisocyanate or an aromatic polyisocyanate; monomer C is a glycol, Trihydric or tetrahydric alcohol.
  • N-alkyldialkylolamine is N-methyldiethanolamine, N-octadecyldiethanolamine or N-methyldimethanolamine ;
  • monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate;
  • monomer C is 1,4-butanediol, 1,4-ethylene glycol;
  • monomer D is 1,3-propyl sultone or 1,4-butyl sultone.
  • a zwitterionic shape memory polyurethane wherein the zwitterionic shape memory polyurethane is prepared by the method for preparing a zwitterionic shape memory polyurethane as described above.
  • the zwitterionic shape memory polyurethane provided by the invention adopts N-alkyl dialkylolamine as a raw material, first prepares polyurethane by a stepwise polymerization method, and then selects a sultone monomer in a tertiary N group.
  • the ring-opening reaction is carried out to introduce a sulfonic acid group on the polyurethane chain, so that the N-alkyldialkylolamine-based polyurethane has both a quaternary ammonium cation and a sulfonic acid anion.
  • the zwitterionic shape memory polyurethane has antibacterial property and biocompatibility because it contains a large amount of quaternary amine cations and sulfonic acid anion groups on the molecular chain; at the same time, the cation anion structure forms a stable physical interaction through ionic interaction.
  • Linking structure, and by adjusting the amount of monomer, the zwitterionic shape memory polyurethane has a suitable glass transition temperature, so that the zwitterionic shape memory polyurethane based on N-alkyldialkylolamine has heat-induced Shape memory performance.
  • the zwitterionic polyurethane also has wet-sensitive shape memory properties or water-sensitive shape memory properties due to the water absorption properties of the anions and cations.
  • FIG. 1 is a view showing the molecular structure of a zwitterionic shape memory polyurethane prepared in Example 1 of the present invention.
  • Example 2 is a DSC chart of different PS amounts of the zwitterionic shape memory polyurethane prepared in Example 1 of the present invention.
  • Example 3 is a triple form of zwitterionic shape memory polyurethane prepared in Example 1 of the present invention; Figure of the memory performance test results.
  • Example 4 is a graph showing the results of the quadruple shape memory performance test of the zwitterionic shape memory polyurethane prepared in Example 2 of the present invention.
  • Example 5 is a self-healing schematic diagram of a zwitterionic shape memory polyurethane prepared in Example 3 of the present invention, wherein a is the initial shape of the initial sample, b is the initial sample divided into two segments, c is a preliminary repair of the two samples, and d is The two samples were completely repaired after drying, e is the microscopic photo showing the interface after the initial repair, and f is the microscopic photograph showing the interface after the complete repair.
  • Fig. 6 is a graph showing the results of cell viability test of zwitterionic shape memory polyurethane prepared in Example 4 of the present invention.
  • Fig. 7 is a graph showing the results of test for the amount of NO radicals produced by the sample of the zwitterionic shape memory polyurethane prepared in Example 5 of the present invention and the mouse macrophage (RAW264.7).
  • Fig. 8 is a graph showing the results of antibacterial properties of the zwitterionic shape memory polyurethane prepared in Example 6 of the present invention.
  • the present invention provides a zwitterionic shape memory polyurethane and a preparation method thereof.
  • the present invention will be further described in detail below in order to clarify and clarify the objects, technical solutions and effects of the present invention. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • the zwitterionic shape memory polyurethane provided by the invention adopts N-alkyldialkylolamine as a raw material, first prepares polyurethane by a stepwise polymerization method, and then selects a sultone monomer to open on a tertiary N group.
  • the ring reaction introduces a sulfonic acid group on the polyurethane chain such that the N-alkyldialkylolamine-based polyurethane has both a quaternary ammonium cation and a sulfonic acid anion.
  • the zwitterionic shape memory polyurethane based on N-alkyldialkylolamine has antibacterial properties and biological properties due to the large amount of quaternary amine cations and sulfonic acid anion groups contained in the molecular chain. Compatible properties; at the same time, the cation structure forms a stable physical crosslink through ionic interaction Structure, and by adjusting the amount of monomer, the zwitterionic shape memory polyurethane has a suitable glass transition temperature, so that the zwitterionic shape memory polyurethane based on N-alkyldialkylolamine has a thermotropic shape Memory performance.
  • the zwitterionic polyurethane also has wet-sensitive shape memory properties or water-sensitive shape memory properties due to the water absorption properties of the anions and cations.
  • the preparation method of the zwitterionic shape memory polyurethane comprises the following steps:
  • Step 1 synthesizing the N-alkyldialkylolamine-based polyurethane from the monomers A and B, or the monomers A, B and C by a stepwise polymerization method;
  • Step 2 synthesizing the zwitterionic shape memory polyurethane by ring-opening reaction of monomer D on the N group of the N-alkyldialkylolamine-based polyurethane.
  • the monomer A is an N-alkyl dialkyl alcohol amine, and its chemical structural formula is as follows:
  • N-alkyldialkylolamine may be N-methyldiethanolamine (MDEA), N-octadecyldiethanolamine (DOEA), N-methyldimethanolamine (MMEA) or the like.
  • Monomer B is a polyisocyanate and may be an aliphatic polyisocyanate or an aromatic polyisocyanate such as hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI). .
  • HDI hexamethylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • the monomer C is a chain extender and is a polyhydric alcohol, and may be a glycol, a triol or a tetrahydric alcohol, such as 1,4-butanediol or 1,4-ethylene glycol.
  • the monomer D is an alkyl sultone, and may be 1,3-propyl sultone (PS) or 1,4-butyl sultone (BS).
  • PS 1,3-propyl sultone
  • BS 1,4-butyl sultone
  • molar ratio of the number of moles of hydroxyl groups [OH] in the monomer A to the number of moles of the isocyanate groups of the monomers B [NCO] is satisfactory, it may not be added.
  • the monomer C is introduced, and therefore, the amount of the monomer C may be zero.
  • step one is as follows:
  • the three-necked flask was charged with monomers A and B, an organic solvent and a catalyst of dibutyltin dilaurate (DBTD). Under mechanical stirring, the reaction was carried out in an oil bath at 70-90 ° C for 2 to 5 hours; Body C, further reacting for 2 to 5 hours to obtain a polyurethane prepolymer solution; adjusting the mass concentration of the polyurethane prepolymer solution with an organic solvent, and controlling it at 10 wt% to 30 wt%.
  • the step of adding the monomer C is not an essential step.
  • step two The specific process of step two is as follows:
  • the polyurethane prepolymer solution prepared in the first step and the metered monomer D were added to the single-mouth flask, and the organic solvent was added to adjust the mass concentration of the mixed solution to 5-20 wt%; then the flask was closed and magnetically stirred.
  • the reaction is carried out in an oil bath of 30 to 50 ° C for 8 to 24 hours. That is, a zwitterionic shape memory polyurethane solution based on an N-alkyldialkylolamine is obtained.
  • the organic solvent is volatilized in a blast oven and a vacuum drying oven at 80 to 100 ° C in this order to obtain a zwitterionic shape memory polyurethane resin and a film.
  • the organic solvent in the first step and the second step may be N,N-dimethylformamide (DMAC), N,N-dimethylacetamide (DMF) or tetrahydrofuran (THF).
  • DMAC N,N-dimethylformamide
  • DMF N,N-dimethylacetamide
  • THF tetrahydrofuran
  • the present invention also provides a zwitterionic shape memory polyurethane which is obtained by the above preparation method.
  • the polyurethane can have an appropriate glass transition temperature by adjusting the amount of the monomer.
  • Adjustable vitrification Shape memory polyurethanes that change temperature to their body temperature can greatly improve the application of shape memory polymers in biomedical, medical, textile and other applications.
  • the zwitterionic shape memory polyurethane has antibacterial properties and biocompatibility properties, and has heat-induced multiple shape memory properties, moisture-sensitive shape memory properties, water-sensitive shape memory properties, and the like, and can also have self-healing properties. performance.
  • the zwitterionic shape memory polyurethane has great application potential in energy materials and biomedical materials.
  • hexamethylene diisocyanate HDI
  • MDEA N-methyldiethanolamine
  • DBTD catalyst dibutyltin dilaurate
  • the ring was reacted for 12 h.
  • the prepared polyurethane/DMF solution was poured into a film holder, dried in a blast oven at 80 ° C for 24 hours, and vacuum dried at 80 ° C for 24 hours to obtain a zwitterionic shape memory polyurethane film.
  • a series of zwitterionic shape memory polyurethanes can be prepared by changing the amount of PS.
  • the molar ratio of 1,3-propane sultone (PS) to MMEA is 0.0, 0.2, 0.4, 0.5, 0.6, 0.8, respectively, at 30 g.
  • a calculated amount of PS was added to a 10 wt.% polyurethane prepolymer solution to obtain a zwitterionic shape memory polyurethane film, and sample numbers ZSMPU0, ZSMPU2, ZSMPU4, ZSMPU5, ZSMPU6, and ZSMPU8 were respectively taken.
  • the DSC curve of zwitterionic polyurethane with different PS content is shown in Fig. 2.
  • the DSC chart shows that the glass transition temperature of polyurethane can be adjusted by the amount of PS. As the amount of PS increases, the glass transition temperature shifts to high temperature.
  • the prepared zwitterionic shape memory polyurethane has triple shape memory properties. As shown in FIG. 3, when the polymer spline is stretched and deformed by 45% at 75 ° C, the fixed shape is changed to 28.5% after being fixed at 50 ° C for a period of time, that is, the first temporary shape is obtained, and the first shape fixing ratio is about 63.2%; After stretching and deforming again to 95% at 50 ° C, after cooling to 0 ° C for a period of time, the shape became 94.2%, that is, the second temporary shape was obtained, and the second shape fixing rate was about 98.8%.
  • the first deformation recovery can be achieved, the deformation is restored from 94.2% to 28.2%, and the first shape recovery rate is about 103%; when the temperature is raised to 75 °C, Achieve the second deformation recovery, the deformation continues to return to 4%, the second shape recovery rate is about 80.81%, and the overall deformation recovery rate is about 95.8%; these results show that the zwitterionic polyurethane has better triple shape memory performance. .
  • the flask was sealed and opened for 24 h.
  • the prepared polyurethane/DMF solution was poured into a film holder, dried in a blast oven at 80 ° C for 24 hours, and vacuum dried at 80 ° C for 24 hours to obtain a zwitterionic shape memory polyurethane film.
  • the quadruple shape memory property of the prepared zwitterionic polyurethane is as shown in Fig. 4.
  • the polymer spline is stretched at 44 ° C for 44%, it is fixed at 73 ° C for a period of time to obtain a fixed shape of 20.3%.
  • the first temporary shape after stretching and deforming again to 67% at 73 ° C, after cooling to 58 ° C for a period of time, the shape becomes 48.9%, which gives a second temporary shape; when stretched again at 58 ° C After the deformation to 85%, after cooling to 0 ° C for a fixed period of time, the shape becomes 84.2%, that is, the third temporary shape is obtained.
  • the first deformation recovery can be achieved, the deformation is restored from 84.2% to 44.8%; when the temperature is continuously increased to 73 ° C, the second under-deformation recovery can be achieved, and the deformation continues to return to 18.2%; when the temperature is raised to 88 ° C, the third under-deformation recovery can be achieved, the deformation continues to return to 6.3%; the total recovery rate reaches 91.60%; indicating that the polymer has better quadruple shape memory properties.
  • a three-necked flask was sequentially charged with 51.3 g of diphenylmethane diisocyanate (MDI), 30 g of N-octadecyldiethanolamine (DOEA) and 0.02 wt.% of catalyst dibutyltin dilaurate (DBTD), 200ml DMF.
  • MDI diphenylmethane diisocyanate
  • DOEA N-octadecyldiethanolamine
  • DBTD catalyst dibutyltin dilaurate
  • the ring was reacted for 24 h.
  • the prepared polyurethane/DMF solution was poured into a film holder, dried in a blast oven at 80 ° C for 24 hours, and vacuum dried at 80 ° C for 24 hours to obtain a zwitterionic shape memory polyurethane film.
  • the vibration peaks of quaternary ammonium salts were also detected; these results indicate the successful preparation of zwitterionic polyurethanes; meanwhile, XPS photoelectron spectroscopy also confirmed the inclusion of S 2S (binding energy, 230 eV) and S 2p in the prepared zwitterionic polyurethane ( Binding energy, 166eV), confirmed that the zwitterionic polyurethane contains a sulfonic acid group; in addition, the N 1s spectrum contains two binding energies, 402 eV belongs to the binding energy of the quaternary amine cation, and 400 eV is the combination of N on the urethane group. Formation, or >N-CH
  • a is the original shape of the zwitterionic polyurethane film, which is cut into two halves
  • b is a zwitterionic polyurethane film.
  • the molar ratio of 1,4-butyl sultone (BS) to MMEA is 0.0, 0.2, 0.4, 0.5, 0.6, 0.8, respectively, and is added to 30 g of the 10 wt.% polyurethane prepolymer solution.
  • the amount of BS was opened in a sealed flask at 50 ° C for 12 h.
  • the prepared polyurethane/DMF solution was poured into a membrane, dried in a blast oven at 80 ° C for 24 hours, and vacuum dried at 80 ° C for 24 hours to obtain a zwitterionic shape memory polyurethane membrane, respectively, taking sample numbers ZSMPU0, ZSMPU2, ZSMPU4, ZSMPU5, ZSMPU6, ZSMPU8.
  • IPDI isophorone diisocyanate
  • MMEA N-methyldimethanolamine
  • DBTD catalyst dibutyltin dilaurate
  • the molar ratio of 1,3-propane sultone (PS) to MMEA is 0.0, 0.2, 0.4, 0.5, 0.6, 0.8, and the calculation amount is added to 30 g of the 10 wt.% polyurethane prepolymer solution, respectively.
  • the PS was opened in a sealed flask at 50 ° C for 12 h.
  • the prepared polyurethane/DMF solution was poured into a membrane, dried in a blast oven at 80 ° C for 24 hours, and vacuum dried at 80 ° C for 24 hours to obtain a zwitterionic shape memory polyurethane membrane, respectively, taking sample numbers ZSMPU0, ZSMPU2, ZSMPU4, ZSMPU5, ZSMPU6, ZSMPU8.
  • a sample of the prepared zwitterionic shape memory polyurethane was cultured with mouse macrophage (RAW264.7), and a mouse macrophage (RAW264.7) was used as a blank control to add bacterial endotoxin (LPS). And mouse macrophage (RAW264.7) as a positive control, the amount of NO radicals produced after treatment is shown in Figure 7, from the figure can be seen that the polymer's NO radical production in the blank structure and bacteria Between the endotoxin, the zwitterionic polyurethane has good biocompatibility.
  • the first step under nitrogen protection, 34.5 g of hexamethylene diisocyanate (HDI), 20 g of N-methyldiethanolamine (MDEA) and 0.02 wt.% of catalyst dibutyltin dilaurate (DBTD) were sequentially added to the three-necked flask. 200ml DMF. The temperature was raised to 80 ° C, the reaction was carried out for 4 hours, and finally the viscosity of the polyurethane prepolymer solution was adjusted to be about 10% by weight. The prepared polyurethane/DMF solution was poured into a membrane, and dried in a blast oven at 80 ° C for 24 hours, and then 80.
  • HDI hexamethylene diisocyanate
  • MDEA N-methyldiethanolamine
  • DBTD catalyst dibutyltin dilaurate
  • the mixture was dried under vacuum for 24 hours to obtain a polyurethane which was not treated with PS, and the sample number was ZSMPU0.
  • the prepared polyurethane/DMF solution was poured into a film holder, dried at 80 ° C for 24 hours in a forced air oven, and vacuum dried at 80 ° C for 24 hours to obtain a zwitterionic shape memory polyurethane film, and the sample number was ZSMPU8.
  • the prepared zwitterionic shape memory polyurethane (ZSMPU8) and the polyurethane without pre-PS (ZSMPU0) were tested for antibacterial properties by a film adhesion method, and no polyurethane was added as a blank control. The results are shown in Fig. 8.
  • Figure 8 shows that the zwitterionic polyurethane has good antibacterial properties, while the antibacterial activity of the polyurethane without PS treatment is very low.
  • the zwitterionic shape memory polyurethane based on the N-alkyldialkylolamine obtained by the preparation method of the zwitterionic shape memory polyurethane provided by the invention has the heat-induced multiple shape memory property, and simultaneously It has antibacterial properties, biocompatible properties and self-healing properties.
  • the zwitterionic shape memory polyurethane has great application potential in engineering, construction, daily life, energy materials and biomedical materials.

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Abstract

本发明公开一种两性离子型形状记忆聚氨酯及其制备方法，所述两性离子型形状记忆聚氨酯，是通过选用N-烷基二烷基醇胺为原料，先通过逐步聚合方法制备聚氨酯，再选用磺酸内酯单体在叔N基团上开环反应，在聚氨酯链上引入磺酸基，使基于N-烷基二烷基醇胺的聚氨酯同时具有季铵阳离子和磺酸阴离子。由于其分子链上同时含有大量季胺阳离子和磺酸阴离子基团，使得所述两性离子型形状记忆聚氨酯具有抗菌性能和生物相容性能。

Description

一种两性离子型形状记忆聚氨酯及其制备方法 技术领域
本发明涉及高分子材料领域，尤其涉及一种两性离子型形状记忆聚氨酯及其制备方法。
背景技术
形状记忆效应是指能够感知环境变化(如温度、力、电磁、溶剂等的刺激)，能够变形并且固定得到临时形状；而在感应外界环境的变化后，又能改变形状回到初始形状。按照刺激条件的不同，形状记忆材料可分为热致敏感型、光致敏感型、电致敏感型及化学感应型等形状记忆材料。目前，聚合物形状记忆材料被广泛应用于纺织，医疗，航空航天，工程等领域。国内外研究者已采用化学和物理的方法开发和应用了多种热致形状记忆聚合物。但普遍综合性能都不够理想，热致形状记忆聚合物若要满足生物医学临床上的应用，需具备与人体体温接近或生物环境相适应的温和刺激条件，以及适度的生物相容性和适宜强度等综合性能。因此，开发出成本较低、加工简单、具有多种性能、生物相容性好的热致形状记忆聚合物是目前理论和应用研究的发展方向。
两性离子聚合物作为高分子材料中的一种，其性质独特，近年来引起了世界范围内的广泛关注。当高分子链同时含有阴离子和阳离子基团时，就称两性离子聚合物，这是一种比较独特的聚电解质。两性离子聚合物因其化学性能好，水化能力强，且不易受溶液值影响，被人们广泛用于生物医用材料，使生命科学得到了迅速的发展。甜菜碱型两性离子型聚合物，是指结构类似天然产物甜菜碱结构，在同一单体结构具有阳离子和阴离子的一类聚合物。甜菜碱型两性离子聚合物因其化学性和热稳定性好、水化 能力强且含有不易受溶液pH值影响的等数目的季铵盐阳离子和磺酸盐阴离子而倍受关注。形状记忆聚合物在生物医疗方面的应用一直是其研究的重点，但是，目前对两性离子聚合物的智能化研究重视不够，具有形状记忆功能的两性离子聚合物研究较少。经临床发现，即使聚氨酯形状记忆聚合物长期植入人体内，也会引起机体的炎症反应。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明中提一种两性离子型形状记忆聚氨酯及其制备方法，基于N-烷基二烷基醇胺的两性离子型形状记忆聚氨酯，具有形状记忆性能和良好生物相容性，旨在解决现有形状记忆聚合物生物相容性不好的问题。
本发明的技术方案如下：
一种两性离子型形状记忆聚氨酯的制备方法，其中，包括以下步骤：
步骤一：由单体A和B通过聚合方法，或者，由单体A、B和C通过逐步聚合方法，合成基于N-烷基二烷基醇胺的聚氨酯；
步骤二：由单体D在所述基于N-烷基二烷基醇胺的聚氨酯的N基团上开环反应，合成所述两性离子型形状记忆聚氨酯；
其中，单体A为N-烷基二烷基醇胺，其化学结构式如下式所示：
Figure PCTCN2015078027-appb-000001
R是-CnHm，n＝1～18，m≤2n+1；R’是CxH2x，x＝1～5；
单体B为多异氰酸酯；单体C为多元醇；单体D为烷基磺酸内酯。
所述的两性离子型形状记忆聚氨酯的制备方法，其中，单体A与单体C的用量满足下列关系:单体A的摩尔数[A]与单体C的摩尔数[C]的摩尔比 例q＝[C]/([C]+[A])为0～0.5；
单体A，单体B与单体C的用量满足下列关系:单体A，或者单体A和C中羟基摩尔数[OH]与单体B异氰酸酯基摩尔数[NCO]的摩尔比例r＝[NCO]/[OH]，为0.95～1.05；
单体D的用量满足下列关系:单体A的摩尔数[A]与单体D的摩尔数[D]的摩尔比例p＝[D]/[A]为0.2～1.2。
所述的两性离子型形状记忆聚氨酯的制备方法，其中，步骤一的具体过程如下：
在氮气保护下，加入单体A、B，有机溶剂以及催化剂二月桂酸二丁基锡，机械搅拌下，在70～90℃反应2～5小时；加入单体C，进一步反应2～5小时，得到聚氨酯预聚体溶液；用有机溶剂调节聚氨酯预聚体溶液质量浓度，控制在10wt％～30wt％。
所述的两性离子型形状记忆聚氨酯的制备方法，其中，步骤二的具体过程如下：
在氮气保护下，所制备的聚氨酯预聚体溶液和计量好的单体D，再加有机溶剂，调节混合溶液质量浓度为5-20wt％；密封，在30～50℃反应8～24小时，得到两性离子型形状记忆聚氨酯溶液。
所述的两性离子型形状记忆聚氨酯的制备方法，其中，步骤二还包括以下步骤：
将两性离子型形状记忆聚氨酯溶液在80～100℃挥发有机溶剂。
所述的两性离子型形状记忆聚氨酯的制备方法，其中，将两性离子型形状记忆聚氨酯溶液依次经过80～100℃的鼓风烘箱和真空干燥箱处理，挥发有机溶剂。
所述的两性离子型形状记忆聚氨酯的制备方法，其中，所述有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或四氢呋喃；
单体B为脂肪族多异氰酸酯或芳香族多异氰酸酯；单体C为二元醇， 三元醇或四元醇。
所述的两性离子型形状记忆聚氨酯的制备方法，其中，所述N-烷基二烷基醇胺为N-甲基二乙醇胺、N-十八烷基二乙醇胺或N-甲基二甲醇胺；单体B为六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯；单体C为1，4-丁二醇、1，4-乙二醇；单体D为1，3-丙基磺酸内酯或1，4-丁基磺酸内酯。
一种两性离子型形状记忆聚氨酯，其中，所述两性离子型形状记忆聚氨酯采用如上所述的两性离子型形状记忆聚氨酯的制备方法制备得到。
有益效果：本发明所提供的两性离子型形状记忆聚氨酯，是通过选用N-烷基二烷基醇胺为原料，先通过逐步聚合方法制备聚氨酯，再选用磺酸内酯单体在叔N基团上开环反应，在聚氨酯链上引入磺酸基，使基于N-烷基二烷基醇胺的聚氨酯同时具有季铵阳离子和磺酸阴离子。由于其分子链上同时含有大量季胺阳离子和磺酸阴离子基团，使得所述两性离子型形状记忆聚氨酯具有抗菌性能和生物相容性能；同时，阳阴离子结构通过离子相互作用，形成稳固物理交联结构，并且可以通过调控单体的用量，使所述两性离子型形状记忆聚氨酯具有适当的玻璃转化温度，从而使基于N-烷基二烷基醇胺的两性离子型形状记忆聚氨酯具有热致形状记忆性能。由于阴阳离子具有吸水性能，也使所述两性离子型聚氨酯具有湿敏感形状记忆性能或水敏感形状记忆性能。
附图说明
图1为本发明实施例1所制备的两性离子型形状记忆聚氨酯的分子结构图。
图2为本发明实施例1所制备的两性离子型形状记忆聚氨酯的不同PS用量的DSC图。
图3为本发明实施例1所制备的两性离子型形状记忆聚氨酯的三重形 状记忆性能测试结果图。
图4为本发明实施例2所制备的两性离子型形状记忆聚氨酯的四重形状记忆性能测试结果图。
图5为本发明实施例3所制备的两性离子型形状记忆聚氨酯的自修复示意图，其中a为初始样品完整形状，b为初始样品分成两段，c为两段样品粘合初步修复，d为两段样品烘干后完全修复，e为显微镜照片显示初步修复后的界面，f为显微镜照片显示完全修复后的界面。
图6为本发明实施例4所制备的两性离子型形状记忆聚氨酯的细胞活性测试结果图。
图7为本发明实施例5所制备的两性离子型形状记忆聚氨酯的样品与小鼠巨噬细胞(RAW264.7)培养后处理的NO自由基生成量测试结果图。
图8为本发明实施例6所制备的两性离子型形状记忆聚氨酯的抗菌性能结果图。
具体实施方式
本发明提供一种两性离子型形状记忆聚氨酯及其制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明所提供的两性离子型形状记忆聚氨酯，是通过选用N-烷基二烷基醇胺为原料，先通过逐步聚合方法制备聚氨酯，再选用磺酸内酯单体在叔N基团上开环反应，在聚氨酯链上引入磺酸基，使基于N-烷基二烷基醇胺的聚氨酯同时具有季铵阳离子和磺酸阴离子。基于N-烷基二烷基醇胺的两性离子型形状记忆聚氨酯，由于其分子链上同时含有大量季胺阳离子和磺酸阴离子基团，使得所述两性离子型形状记忆聚氨酯具有抗菌性能和生物相容性能；同时，阳阴离子结构通过离子相互作用，形成稳固物理交联 结构，并且可以通过调控单体的用量，使所述两性离子型形状记忆聚氨酯具有适当的玻璃转化温度，从而使基于N-烷基二烷基醇胺的两性离子型形状记忆聚氨酯具有热致形状记忆性能。由于阴阳离子具有吸水性能，也使所述两性离子型聚氨酯具有湿敏感形状记忆性能或水敏感形状记忆性能。
具体地，所述两性离子型形状记忆聚氨酯的制备方法包括以下步骤：
步骤一：由单体A和B，或者，单体A、B和C通过逐步聚合方法合成基于N-烷基二烷基醇胺的聚氨酯；
步骤二：由单体D在所述基于N-烷基二烷基醇胺的聚氨酯的N基团上开环反应，合成所述两性离子型形状记忆聚氨酯。
其中，单体A为N-烷基二烷基醇胺，其化学结构式如下式所示：
Figure PCTCN2015078027-appb-000002
其中，R是-CnHm(n＝1～18，m≤2n+1)；R’是CxH2x(x＝1～5)。所述N-烷基二烷基醇胺可以为N-甲基二乙醇胺(MDEA)、N-十八烷基二乙醇胺(DOEA)、N-甲基二甲醇胺(MMEA)等。
单体B为多异氰酸酯，可以为脂肪族多异氰酸酯或芳香族多异氰酸酯等，如六亚甲基二异氰酸酯(HDI)、二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)。
单体C为扩链剂，为多元醇，可以为二元醇，三元醇或四元醇等，如1，4-丁二醇、1，4-乙二醇。
单体D为烷基磺酸内酯，可以为1，3-丙基磺酸内酯(PS)或1，4-丁基磺酸内酯(BS)等。
单体A与单体C的用量满足下列关系:单体A的摩尔数[A]与单体C的摩尔数[C]的摩尔比例q＝[C]/([C]+[A])为0～0.5。当单体A中羟基摩尔数[OH]与单体B异氰酸酯基摩尔数[NCO]的摩尔比例满足要求时，可以不加 入单体C，因此，单体C的用量可以为0。
单体A，单体B与单体C的用量满足下列关系:单体A，或者单体A和C中羟基摩尔数[OH]与单体B异氰酸酯基摩尔数[NCO]的摩尔比例r＝[NCO]/[OH]，为0.95～1.05。
单体D的用量满足下列关系:单体A的摩尔数[A]与单体D的摩尔数[D]的摩尔比例p＝[D]/[A]为0.2～1.2。
进一步地，步骤一的具体过程如下：
在氮气保护下，三口烧瓶中加入单体A、B，有机溶剂以及催化剂二月桂酸二丁基锡(DBTD)，机械搅拌下，在70～90℃油浴中，反应2～5小时；再加入单体C，进一步反应2～5小时，得到聚氨酯预聚体溶液；用有机溶剂调节聚氨酯预聚体溶液质量浓度，控制在10wt％～30wt％。其中，加入单体C这一步骤不是必要步骤，如果单体A中羟基摩尔数[OH]与单体B异氰酸酯基摩尔数[NCO]的摩尔比例满足要求时，即不需要加入单体C，当单体A与B反应完后，就可得到聚氨酯预聚体溶液。
步骤二的具体过程如下：
在氮气保护下，单口烧瓶中加入第一步所制备的聚氨酯预聚体溶液和计量好的单体D，再加有机溶剂，调节混合溶液质量浓度为5-20wt％；然后密闭烧瓶，磁力搅拌下，在30～50℃油浴中，反应8～24小时。即得基于N-烷基二烷基醇胺的两性离子型形状记忆聚氨酯溶液。最后，依次在80～100℃鼓风烘箱和真空干燥箱中挥发有机溶剂，即可制得两性离子型形状记忆聚氨酯树脂和膜材等。
其中，步骤一和步骤二中所述有机溶剂可以为N,N-二甲基甲酰胺(DMAC)，N,N-二甲基乙酰胺(DMF)或四氢呋喃(THF)。
本发明中还提供一种两性离子型形状记忆聚氨酯，是采用上述制备方法得到的。基于N-烷基二烷基醇胺的两性离子型形状记忆聚氨酯，可以通过调控单体的用量，使聚氨酯具有适当的玻璃转化温度。可调控玻璃化转 变温度，使其接近人体温度的形状记忆聚氨酯可以大大提高形状记忆聚合物在生物医药，医疗，纺织等方面的应用。而且，所述两性离子型形状记忆聚氨酯还具有抗菌性能和生物相容性能，同时，具有热致多重形状记忆性能、湿敏感形状记忆性能、水敏感形状记忆性能等，另外，还可具有自修复性能。所述两性离子型形状记忆聚氨酯在能源材料以及生物医用材料等方面都具有巨大的应用潜能。
实施例1
第一步，在氮气保护下，三口烧瓶中依次加入34.5g六亚甲基二异氰酸酯(HDI)，20g N-甲基二乙醇胺(MDEA)和0.02wt.％催化剂二月桂酸二丁基锡(DBTD)，200ml DMF。温度升至80℃，反应4小时，最后调节聚氨酯预聚体溶液粘度约为10wt％。第二步，按1,3-丙磺酸内酯(PS)与MDEA摩尔比为0.2(r＝0.2)，在30g含10wt.％聚氨酯预聚体溶液中加入0.15gPS，在50℃的密封烧瓶中，开环反应12h。将所制备的聚氨酯/DMF溶液倒在膜具中，在80℃鼓风烘箱干燥的24小时，再80℃真空干燥24小时，获得两性离子形状记忆聚氨酯膜材。
所制备的两性离子聚氨酯分子结构如图1所示，红外光谱表明3318cm-1处有N-H振动峰，1688cm-1有C＝O振动峰，表明氨酯健的成功形成；另外，在1038cm-1还检测出SO3 -基团的峰；960cm-1还检测出季胺盐的振动峰；这些结果表明了两性离子聚氨酯的成功制备；同时，XPS光电子能谱也证实在所制备的两性离子聚氨酯中含有S2S(结合能,230eV)and S2p(结合能,166eV)，证实该两性离子聚氨酯含磺酸基团；另外，N1s谱图中含有两种结合能，402eV属于季胺阳离子的结合能，而400eV f是氨酯基团上N的结合成，或没有完全反应的>N-CH3；这些结果充分证实本实例成功制备了含阴离子和阳离子基团的两性离子聚氨酯。
改变PS用量可以制备一系列两性离子形状记忆聚氨酯，按1,3-丙磺酸内酯(PS)与MMEA摩尔比为0.0，0.2，0.4，0.5，0.6，0.8，分别在30g 含10wt.％聚氨酯预聚体溶液中加入计算量的PS，获得两性离子形状记忆聚氨酯膜材，分别取样品号ZSMPU0,ZSMPU2,ZSMPU4,ZSMPU5,ZSMPU6,ZSMPU8。不同PS含量的两性离子聚氨酯的DSC曲线如图2所示，DSC图表明聚氨酯的玻璃转化温度可以通过PS用量进行调节，随着PS量增加，玻璃转化温度向高温移动。
所制备的两性离子形状记忆聚氨酯具有三重形状记忆性能。如图3所示，当聚合物样条在75℃拉伸变形45％后，于50℃固定一段时间后得到固定形变为28.5％，即得第一次临时形状，第一次形状固定率约63.2％；当在50℃下再次拉伸变形至95％后，降温到0℃固定一段时间后得形变为94.2％，即得第二次临时形状，第二次形状固定率约98.8％。当温度从0℃升高至50℃时，可以实现第一次形变回复，形变从94.2％回复至28.2％，实现第一次形状回复率约103％；继续升高温度至75℃时，可以实现第二次形变回复，形变继续回复至4％，实现第二次形状回复率约80.81％，而整体形变回复率约为95.8％；这些结果表明该两性离子聚氨酯具有较好的三重形状记忆性能。
实施例2
第一步，在氮气保护下，三口烧瓶中依次加入34.5g六亚甲基二异氰酸酯(HDI)，10g N-甲基二乙醇胺(MDEA)和0.02wt.％催化剂二月桂酸二丁基锡(DBTD)，200ml DMF。温度升至70℃，反应4小时；然后再加入9g1，4-丁二醇反应4小时。最后调节聚氨酯预聚体溶液粘度约为10wt％。第二步，按1,4-丁基磺酸内酯(BS)与MDEA摩尔比为0.4(r＝0.4)，在30g含10wt.％聚氨酯预聚体溶液中加入0.15gBS，在40℃的密封烧瓶中，开环反应24h。将所制备的聚氨酯/DMF溶液倒在膜具中，在80℃鼓风烘箱干燥的24小时，再80℃真空干燥24小时，获得两性离子形状记忆聚氨酯膜材。
红外光谱表明3319cm-1处有N-H振动峰，1695cm-1有C＝O振动峰， 表明氨酯健的成功形成；另外，在1037cm-1还检测出SO3 -基团的峰；965cm-1还检测出季胺盐的振动峰；这些结果表明了两性离子聚氨酯的成功制备；同时，XPS光电子能谱也证实在所制备的两性离子聚氨酯中含有S2S(结合能,230eV)and S2p(结合能,166eV)，证实该两性离子聚氨酯含磺酸基团；另外，N1s谱图中含有两种结合能，402eV属于季胺阳离子的结合能，而400eV是氨酯基团上N的结合成，或没有完全反应的>N-CH3；这些结果充分证实本实例成功制备了含阴离子和阳离子基团的两性离子聚氨酯。
所制备的两性离子型聚氨酯的四重形状记忆性能如图4所示，当聚合物样条在88℃拉伸变形44％后，于73℃固定一段时间后得到固定形变为20.3％，即得第一次临时形状；当在73℃下再次拉伸变形至67％后，降温到58℃固定一段时间后得形变为48.9％，即得第二次临时形状；当在58℃下再次拉伸变形至85％后，降温到0℃固定一段时间后得形变为84.2％，即得第三次临时形状。当温度从0℃升高至58℃时，可以实现第一次形变回复，形变从84.2％回复至44.8％；继续升高温度至73℃时，可以实现第二欠形变回复，形变继续回复至18.2％；继续升高温度至88℃时，可以实现第三欠形变回复，形变继续回复至6.3％；总的回复率达到了91.60％；表明该聚合物具有较好的四重形状记忆性能。
实施例3
第一步，在氮气保护下，三口烧瓶中依次加入51.3g二苯基甲烷二异氰酸酯(MDI)，30g N-十八烷基二乙醇胺(DOEA)和0.02wt.％催化剂二月桂酸二丁基锡(DBTD)，200ml DMF。温度升至70℃，反应4小时，最后调节聚氨酯预聚体溶液粘度约为10wt％。第二步，按1,3-丙磺酸内酯(PS)与DOEA摩尔比为0.8(r＝0.8)，在30g含10wt.％聚氨酯预聚体溶液中加入0.60gPS，在50℃的密封烧瓶中，开环反应24h。将所制备的聚氨酯/DMF溶液倒在膜具中，在80℃鼓风烘箱干燥的24小时，再80℃真空干燥24小时，获得两性离子形状记忆聚氨酯膜材。
红外光谱表明3316cm-1处有N-H振动峰，1698cm-1有C＝O振动峰，表明氨酯健的成功形成；另外，在1035cm-1还检测出SO3 -基团的峰；966cm-1还检测出季胺盐的振动峰；这些结果表明了两性离子聚氨酯的成功制备；同时，XPS光电子能谱也证实在所制备的两性离子聚氨酯中含有S2S(结合能,230eV)and S2p(结合能,166eV)，证实该两性离子聚氨酯含磺酸基团；另外，N1s谱图中含有两种结合能，402eV属于季胺阳离子的结合能，而400eV是氨酯基团上N的结合成，或没有完全反应的>N-CH3；这些结果充分证实本实例成功制备了含阴离子和阳离子基团的两性离子聚氨酯。
所制备的两性离子型聚氨酯的自修复性能如图5所示，图5中a图为所述两性离子型聚氨酯膜材原始形状，对其进行切割分成两半，b图为两性离子型聚氨酯膜材切割后的形状；将两半两性离子型聚氨酯切口靠近，一段时间后，切口开始融合，如c图和e图所示；最后，切口完全复合，如d图和f图所示。
实施例4
第一步，在氮气保护下，三口烧瓶中依次加入34.5g六亚甲基二异氰酸酯(HDI)，8gN-甲基二甲醇胺(MMEA)和0.02wt.％催化剂二月桂酸二丁基锡(DBTD)，200ml DMF。温度升至70℃，反应3小时，然后再加入9g1，4-乙二醇反应3小时；最后调节聚氨酯预聚体溶液粘度约为10wt％。第二步，按1,4-丁基磺酸内酯(BS)与MMEA摩尔比为0.0，0.2，0.4，0.5，0.6，0.8，分别在30g含10wt.％聚氨酯预聚体溶液中加入计算量的BS，在50℃的密封烧瓶中，开环反应12h。将所制备的聚氨酯/DMF溶液倒在膜具中，在80℃鼓风烘箱干燥的24小时，再80℃真空干燥24小时，获得两性离子形状记忆聚氨酯膜材，分别取样品号ZSMPU0,ZSMPU2,ZSMPU4,ZSMPU5,ZSMPU6,ZSMPU8。
所制备的两性离子型形状记忆聚氨酯的样品与小鼠巨噬细胞(RAW264.7)培养后处理的CCK-8测试结果，如图6所示，从图中可以看 出，没有聚氨酯处理空白小鼠巨噬细胞活性为100％，而PS处理的两性离子形状记忆聚氨酯的活性在78.4％至101.8％,且随着PS用量增加，活性增加，这些结果表明两性离子聚氨酯具有较好的生物相容性。
实施例5
第一步，在氮气保护下，三口烧瓶中依次加入45g异佛尔酮二异氰酸酯(IPDI)，8gN-甲基二甲醇胺(MMEA)和0.02wt.％催化剂二月桂酸二丁基锡(DBTD)，200ml DMF。温度升至70℃，反应5小时；最后调节聚氨酯预聚体溶液粘度约为10wt％。第二步，按1,3-丙磺酸内酯(PS)与MMEA摩尔比为0.0，0.2，0.4，0.5，0.6，0.8，分别在30g含10wt.％聚氨酯预聚体溶液中加入计算量的PS，在50℃的密封烧瓶中，开环反应12h。将所制备的聚氨酯/DMF溶液倒在膜具中，在80℃鼓风烘箱干燥的24小时，再80℃真空干燥24小时，获得两性离子形状记忆聚氨酯膜材，分别取样品号ZSMPU0,ZSMPU2,ZSMPU4,ZSMPU5,ZSMPU6,ZSMPU8。
所制备的两性离子型形状记忆聚氨酯的样品与小鼠巨噬细胞(RAW264.7)培养，同时以单纯的小鼠巨噬细胞(RAW264.7)作为空白对照，以加入细菌内毒素(LPS)和小鼠巨噬细胞(RAW264.7)作为阳性对照，经过处理后的NO自由基生成量如图7所示，从图中可以看出该聚合物的NO自由基生成量在空白结构与细菌内毒素之间，表明该两性离子聚氨酯具有较好的生物相容性。
实施例6
第一步，在氮气保护下，三口烧瓶中依次加入34.5g六亚甲基二异氰酸酯(HDI)，20gN-甲基二乙醇胺(MDEA)和0.02wt.％催化剂二月桂酸二丁基锡(DBTD)，200ml DMF。温度升至80℃，反应4小时，最后调节聚氨酯预聚体溶液粘度约为10wt％，将所制备的聚氨酯/DMF溶液倒在膜具中，在80℃鼓风烘箱干燥的24小时，再80℃真空干燥24小时，获得未PS处理的聚氨酯，取样品号为ZSMPU0。第二步，按1,3-丙磺酸内酯(PS)与 MDEA摩尔比为0.8(r＝0.8)，在30g含10wt.％聚氨酯预聚体溶液中加入0.60gPS，在50℃的密封烧瓶中，开环反应12h。将所制备的聚氨酯/DMF溶液倒在膜具中，在80℃鼓风烘箱干燥的24小时，再80℃真空干燥24小时，获得两性离子形状记忆聚氨酯膜，取样品号为ZSMPU8。
所制备的两性离子型形状记忆聚氨酯(ZSMPU8)与没有PS前的聚氨酯(ZSMPU0)，用薄膜密着法测抗菌性能，以不添加聚氨酯为空白对照(control)，结果如图8所示。图8表明两性离子聚氨酯具有较好的抗菌性能，而没有PS处理的聚氨酯抗菌活性很低。
从上述实施例看到，采用本发明所提供的两性离子形状记忆聚氨酯的制备方法得到的基于N-烷基二烷基醇胺的两性离子型形状记忆聚氨酯，具有热致多重形状记忆性能，同时，具有抗菌性能、生物相容性能以及自修复性能。所述两性离子型形状记忆聚氨酯在工程、建筑、日常生活、能源材料以及生物医用材料等方面都具有巨大的应用潜能。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (9)

  1. 一种两性离子型形状记忆聚氨酯的制备方法，其特征在于，包括以下步骤：
    步骤一：由单体A和B通过聚合方法，或者，由单体A、B和C通过逐步聚合方法，合成基于N-烷基二烷基醇胺的聚氨酯；
    步骤二：由单体D在所述基于N-烷基二烷基醇胺的聚氨酯的N基团上开环反应，合成所述两性离子型形状记忆聚氨酯；
    其中，单体A为N-烷基二烷基醇胺，其化学结构式如下式所示：
    Figure PCTCN2015078027-appb-100001
    R是-CnHm，n＝1～18，m≤2n+1；R’是CxH2x，x＝1～5；
    单体B为多异氰酸酯；单体C为多元醇；单体D为烷基磺酸内酯。
  2. 根据权利要求1所述的两性离子型形状记忆聚氨酯的制备方法，其特征在于，单体A与单体C的用量满足下列关系:单体A的摩尔数[A]与单体C的摩尔数[C]的摩尔比例q＝[C]/([C]+[A])为0～0.5；
    单体A，单体B与单体C的用量满足下列关系:单体A，或者单体A和C中羟基摩尔数[OH]与单体B异氰酸酯基摩尔数[NCO]的摩尔比例r＝[NCO]/[OH]，为0.95～1.05；
    单体D的用量满足下列关系:单体A的摩尔数[A]与单体D的摩尔数[D]的摩尔比例p＝[D]/[A]为0.2～1.2。
  3. 根据权利要求1所述的两性离子型形状记忆聚氨酯的制备方法，其特征在于，步骤一的具体过程如下：
    在氮气保护下，加入单体A、B，有机溶剂以及催化剂二月桂酸二丁基锡，机械搅拌下，在70～90℃反应2～5小时；加入单体C，进一步反应2～5小时，得到聚氨酯预聚体溶液；用有机溶剂调节聚氨酯预聚体溶液质量浓 度，控制在10wt％～30wt％。
  4. 根据权利要求1所述的两性离子型形状记忆聚氨酯的制备方法，其特征在于，步骤二的具体过程如下：
    在氮气保护下，所制备的聚氨酯预聚体溶液和计量好的单体D，再加有机溶剂，调节混合溶液质量浓度为5-20wt％；密封，在30～50℃反应8～24小时，得到两性离子型形状记忆聚氨酯溶液。
  5. 根据权利要求4所述的两性离子型形状记忆聚氨酯的制备方法，其特征在于，步骤二还包括以下步骤：
    将两性离子型形状记忆聚氨酯溶液在80～100℃挥发有机溶剂。
  6. 根据权利要求5所述的两性离子型形状记忆聚氨酯的制备方法，其特征在于，将两性离子型形状记忆聚氨酯溶液依次经过80～100℃的鼓风烘箱和真空干燥箱处理，挥发有机溶剂。
  7. 根据权利要求3或4所述的两性离子型形状记忆聚氨酯的制备方法，其特征在于，所述有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或四氢呋喃；
    单体B为脂肪族多异氰酸酯或芳香族多异氰酸酯；单体C为二元醇，三元醇或四元醇。
  8. 根据权利要求1～7任一所述的两性离子型形状记忆聚氨酯的制备方法，其特征在于，所述N-烷基二烷基醇胺为N-甲基二乙醇胺、N-十八烷基二乙醇胺或N-甲基二甲醇胺；单体B为六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯；单体C为1，4-丁二醇、1，4-乙二醇；单体D为1，3-丙基磺酸内酯或1，4-丁基磺酸内酯。
  9. 一种两性离子型形状记忆聚氨酯，其特征在于，所述两性离子型形状记忆聚氨酯采用如权利要求1～8任一所述的两性离子型形状记忆聚氨酯的制备方法制备得到。
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