WO2019100195A1 - 一种聚氨酯水凝胶的制备方法 - Google Patents

一种聚氨酯水凝胶的制备方法 Download PDF

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WO2019100195A1
WO2019100195A1 PCT/CN2017/112074 CN2017112074W WO2019100195A1 WO 2019100195 A1 WO2019100195 A1 WO 2019100195A1 CN 2017112074 W CN2017112074 W CN 2017112074W WO 2019100195 A1 WO2019100195 A1 WO 2019100195A1
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polyurethane
hours
acetone
room temperature
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PCT/CN2017/112074
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French (fr)
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陈少军
王彩
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深圳大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the invention belongs to the technical field of polymer material preparation, and in particular relates to a preparation method of a polyurethane hydrogel.
  • the polyurethane (PU) structure contains a large number of repeating urethane segments, and the macromolecular backbone is composed of a soft segment composed of an oligomer polyol and a hard segment composed of a polyisocyanate and a small molecular chain extender. of.
  • the macromolecular chain of polyurethane since the hardness of the hard segment is strong, the attraction between each other is large, and the hard segment and the soft segment have a tendency to spontaneously phase separate. Therefore, the polyurethane hard segments are easily gathered together and distributed in the soft segment phase to form a microphase separation structure. It is the physical properties of this microphase separation of polyurethane that makes it superior to other polymer materials in physical and mechanical properties, anticoagulant properties, biocompatibility and other characteristics.
  • Hydrogels are a class of polymers that have a three-dimensional network structure that is water-swellable but insoluble in water. It swells in water to an equilibrium volume and still retains its original structural form.
  • Polyurethane hydrogel has the advantages of both polyurethane and hydrogel, and is widely used in biomedical fields, such as drug delivery vehicles, contact lenses, tissue filling materials, wound dressings, medical sensors, and the like. Due to the excellent properties of the above polyurethanes and hydrogels, polyurethane hydrogels combine the excellent properties of both and can be applied to various technical fields.
  • the preparation method of the polyurethane hydrogel is obtained by reacting a diisocyanate with a polyethylene glycol to obtain a polyurethane prepolymer, and then polymerizing and solidifying with a small molecular chain extender or a crosslinking agent to obtain a polyurethane elastomer or prepolymerization. The body is then swollen in water or an organic solvent to form a polyurethane hydrogel.
  • the preparation process of this kind of method is cumbersome, and it is necessary to add a chemical crosslinking agent, an organic solvent or a photoinitiator, etc. These reagents have more or less certain toxicity, which may cause different degrees of pollution to the material itself and the external environment.
  • the invention provides a preparation method of a polyurethane hydrogel, which aims to solve the problem that the existing preparation method is cumbersome and the added reagent causes pollution.
  • the invention provides a preparation method of a polyurethane hydrogel, comprising:
  • the dehydrated polyol and polyisocyanate are added to the catalyst and heated under nitrogen to 70 ⁇ 90 ° C for 2 ⁇ 4h;
  • the reaction system is cooled to 40 ⁇ 50 ° C, 2,2-dimethylolpropionic acid is added and diluted with acetone for 0.5 ⁇ 1.5h, wherein the mass of the 2,2-dimethylolpropionic acid and the polyol The ratio is 1:10 ⁇ 20, and the volume ratio of acetone to the reaction system is 0.1 ⁇ 1:1;
  • the reaction system was cooled to room temperature, and the organic alkali solution triethylamine was added and neutralized for 10-20 min. Under high-speed stirring, water dispersion was added dropwise, and acetone was distilled off under reduced pressure for 2 hours to obtain an aqueous polyurethane emulsion, wherein the quality of triethylamine was The molar ratio of 2,2-dimethylolpropionic acid is 1:2 ⁇ 3;
  • the aqueous polyurethane emulsion and the polyvinyl alcohol solution are mixed at a mass ratio of 1 to 45:10, and frozen at -25 ° C for 8 to 12 hours, and then thawed at room temperature for 4 to 6 hours, and repeatedly frozen and thawed several times to obtain Polyurethane hydrogel.
  • the mass fraction of the polyvinyl alcohol solution is 12.5%.
  • the invention provides a preparation method of a polyurethane hydrogel.
  • the invention obtains a polyurethane hydrogel by mixing the prepared aqueous polyurethane solution with a polyvinyl alcohol solution, and after multiple freezing and thawing, the preparation method avoids using a large amount of organic Solvents, chemical crosslinkers, and photoinitiators do not cause reagent contamination.
  • the method is simple in operation, controllable in conditions, and suitable for large-scale use.
  • Figure 1 is a scanning electron microscopy test chart of a polyurethane hydrogel prepared in Example 1 of the present invention.
  • the invention provides a preparation method of a polyurethane hydrogel, the method mainly comprising the following steps:
  • Step 1 according to the mass ratio of 1 ⁇ 7:1, the dehydrated polyol and polyisocyanate are added to the catalyst under nitrogen atmosphere to 70 ⁇ 90 ° C for 2 ⁇ 4h;
  • Step 2 the reaction system is cooled to 40 ⁇ 50 ° C, and 2,2-dimethylolpropionic acid and acetone are added to react for 0.5 to 1.5 hours;
  • the mass ratio of 2,2-dimethylolpropionic acid to polyol is 1:10-20, and the volume ratio of acetone to reaction system is 0.1 ⁇ 1:1.
  • Step 3 The reaction system is cooled to room temperature, the organic alkali solution triethylamine is added, neutralized for 10-20 min, stirred at high speed, water is dispersed dropwise, and acetone is removed by distillation under reduced pressure for 2 h to obtain an aqueous polyurethane emulsion.
  • the molar ratio of the mass of the triethylamine to the 2,2-dimethylolpropionic acid is 1:2 to 3.
  • Step 4 mixing the aqueous polyurethane solution with the polyvinyl alcohol solution according to a mass ratio of 1 to 45:10, and freezing at -25 ° C for 8 to 12 hours, and then thawing at room temperature for 4 to 6 hours, repeatedly freezing and thawing Next, a polyurethane hydrogel was obtained in which the mass fraction of the polyvinyl alcohol solution was 12.5%.
  • the invention provides a preparation method of a polyurethane hydrogel.
  • the invention obtains a polyurethane hydrogel by mixing the prepared aqueous polyurethane solution with a polyvinyl alcohol solution, and after repeatedly freezing and thawing, the preparation method avoids using a large amount of Organic solvents, chemical crosslinkers, and photoinitiators do not cause reagent contamination.
  • the method is simple in operation, controllable in conditions, and suitable for large-scale use.
  • the polyol in the first step is at least one of a castor oil-based diol, a polyether diol, a polycaprolactone ethylene glycol, a polyethylene glycol, and a polytetrahydrofuran ether diol
  • the polyisocyanate includes 4 At least one of 4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate.
  • the polyol can be vacuum-dehydrated at 100 ° C, and the polyol is heated and reacted in a three-necked flask equipped with a stirrer, a condensing reflux tube, and nitrogen with a polyisocyanate.
  • the heating temperature is 70 ° C and the reaction time is 3 h. At this time, the content of -NCO in the reaction system is 10%.
  • the temperature is lowered to 50 ° C by using ice water, and the viscosity of the system can be lowered by adding acetone.
  • the reaction system is cooled to room temperature, and triethylamine is added to neutralize the carboxyl functional group in the system. And under high-speed stirring at 800 ⁇ 1000r/min, deionized water was slowly added dropwise for dispersion.
  • the obtained solution was placed in a rotary evaporator at a temperature of 45 to 55 ° C and a pressure of 0.08 to 0.1 MPa, and distilled under reduced pressure for 2 hours.
  • the acetone content was 0.5%, an aqueous polyurethane emulsion was obtained.
  • the fourth step 100 g of polyvinyl alcohol is added to the flask, 700 mL of distilled water is added, and the reaction is carried out for 3 to 4 hours in a water bath at 90 ° C until the PVA is completely dissolved, thereby obtaining a PVA having a clear transparent mass fraction of 12.5%.
  • Aqueous solution The PVA solution was slowly added dropwise to the aqueous polyurethane emulsion, wherein the mass ratio of the two was 1 to 45:10. It is preferably 1:1.
  • the mixture is frozen at -25 ° C for 8 to 12 hours, then thawed at 25 ° C for 4 to 8 hours, reciprocated so frozen and thawed 3 to 5 times, after the last thaw, placed on a freeze dryer for at least 24 h. Until the moisture in the gel is completely drained, a polyurethane porous material is obtained.
  • the material is a porous composite high liquid absorbing material with excellent mechanical properties, non-toxic biocompatible properties and tear resistance.
  • the polyether diol (molecular weight 4800) was purged with nitrogen in a three-necked flask, heated to 100 ° C, and vacuumed for 2 h, then added 5.25 g of 4,4'-diphenylmethane diisocyanate (MDI), 0.12 g of triethylene.
  • MDI 4,4'-diphenylmethane diisocyanate
  • the diamine catalyst was reacted at 70 ° C for 2 h to obtain a polyurethane prepolymer.
  • the polyurethane prepolymer was cooled to 50 ° C, and 1.25 g of 2,2-dimethylolpropionic acid (DMPA) and 40 mL of acetone were added to reduce the viscosity of the system for 2 h. After completion of the reaction, the temperature was lowered to room temperature, 0.75 g of triethylamine was added, and the reaction was neutralized for 15 min. Finally, under high-speed stirring at 1000r/min, deionized water was slowly added dropwise for dispersion, placed in a rotary evaporator, and distilled under reduced pressure at 45 ° C and 0.09 MPa for 2 h to an acetone content of 0.5% to obtain a milky white waterborne polyurethane.
  • Emulsion (WPU) Emulsion
  • the prepared WPU emulsion was weighed into 1.2 g in a beaker, and subjected to high-speed magnetic stirring, and 10 g of an aqueous PVA solution was gradually added thereto, and after 30 minutes, a uniformly mixed mixture was obtained.
  • the mixture was poured into a mold of a 24-well plate, frozen at -25 ° C for 12 hours, and thawed at room temperature for 6 hours, and repeatedly lyophilized 5 times under the above conditions. After the fifth thawing, it was frozen at -25 ° C for 5 hours until the flowing water in the gel was completely solidified, and then freeze-dried in a freeze dryer for 48 hours until the water in the gel was completely drained to obtain a dry Polyurethane hydrogel material.
  • FIG. 1 is a scanning electron microscope test chart of the polyurethane hydrogel material prepared in Example 1, wherein it can be seen from the figure that the surface of the material is a porous structure.
  • the polyurethane prepolymer was cooled to 50 ° C, 2.3 g of 2,2-dimethylolpropionic acid (DMPA) and 30 mL of acetone were added to reduce the viscosity of the system, and the reaction was carried out for 2 h. After completion of the reaction, the temperature was lowered to room temperature, 1.25 g of triethylamine was added, and the reaction was neutralized for 15 min. Finally, under high-speed stirring at 800r/min, deionized water was slowly added dropwise for dispersion, placed in a rotary evaporator, and distilled under reduced pressure at 45 ° C and 0.09 MPa for 2 h to an acetone content of 0.5% to obtain a pale blue color.
  • WPU Waterborne polyurethane emulsion
  • the prepared WPU emulsion was weighed into 4.6 g in a beaker, and subjected to high-speed magnetic stirring, and 10 g of an aqueous PVA solution was gradually added thereto, and after 30 minutes, a uniformly mixed mixture was obtained.
  • the mixture was poured into a mold of a 24-well plate, and frozen at -20 ° C for 12 hours, and at room temperature for 6 hours, and repeatedly defrosted 5 times under the above conditions. After the fifth thawing, it was frozen at -25 ° C for 5 hours until the flowing water in the gel was completely solidified, and then freeze-dried in a freeze dryer for 48 hours until the water in the gel was completely drained to obtain a dry Polyurethane hydrogel material.
  • the polyurethane prepolymer was cooled to 50 ° C, 1.5 g of 2,2-dimethylolpropionic acid (DMPA) and 40 mL of acetone were added to reduce the viscosity of the system, and the reaction was carried out for 2 h. After completion of the reaction, the temperature was lowered to room temperature, 1.2 g of triethylamine was added, and the reaction was neutralized for 15 min. Finally, under high-speed stirring at 1000r/min, deionized water was slowly added dropwise for dispersion, placed in a rotary evaporator, and distilled under reduced pressure at 45 ° C and 0.09 MPa for 2 h to an acetone content of 0.5% to obtain a white water-based polyurethane.
  • Emulsion (WPU) Emulsion
  • the obtained WPU emulsion was weighed to 10.8 g in a beaker, and subjected to high-speed magnetic stirring, and 10 g of an aqueous PVA solution was gradually added thereto, and after 30 minutes, a uniformly mixed mixture was obtained.
  • the mixture was poured into a mold of a 24-well plate, frozen at -25 ° C for 12 hours, and thawed at room temperature for 6 hours, and repeatedly lyophilized 5 times under the above conditions. After the fifth thawing, it was frozen at -25 ° C for 5 hours until the flowing water in the gel was completely solidified, and then freeze-dried in a freeze dryer for 48 hours until the water in the gel was completely drained to obtain a dry Polyurethane hydrogel material.
  • the polyurethane prepolymer was cooled to 50 ° C, 1.3 g of 2,2-dimethylolpropionic acid (DMPA) and 30 mL of acetone were added to reduce the viscosity of the system, and the reaction was carried out for 2 h. After completion of the reaction, the temperature was lowered to room temperature, 0.5 g of triethylamine was added, and the reaction was neutralized for 15 min. Finally, under high-speed stirring at 800r/min, deionized water was slowly added dropwise for dispersion, placed in a rotary evaporator, and distilled under reduced pressure at 45 ° C and 0.09 MPa for 2 h to an acetone content of 0.5% to obtain a white water-based polyurethane.
  • the prepared WPU emulsion was weighed into 25.2 g in a beaker, and subjected to high-speed magnetic stirring, and 10 g of an aqueous PVA solution was gradually added thereto, and after 30 minutes, a uniformly mixed mixture was obtained.
  • the mixture was poured into a mold of a 24-well plate, frozen at -25 ° C for 12 hours, and thawed at room temperature for 6 hours, and repeatedly lyophilized 5 times under the above conditions. After the fifth thawing, it was frozen at -25 ° C for 5 hours until the flowing water in the gel was completely solidified, and then freeze-dried in a freeze dryer for 48 hours until the water in the gel was completely drained to obtain a dry Polyurethane hydrogel material.
  • the polyurethane prepolymer was cooled to 50 ° C, and the reaction system was diluted by adding 0.75 g of 2,2-dimethylolpropionic acid (DMPA) and 40 mL of acetone for 2 h. After completion of the reaction, the temperature was lowered to room temperature, 0.45 g of triethylamine was added, and the reaction was neutralized for 15 min. Finally, under high-speed stirring at 1000r/min, deionized water was slowly added dropwise for dispersion, placed in a rotary evaporator, and distilled under reduced pressure at 45 ° C and 0.09 MPa for 2 h to an acetone content of 0.5% to obtain a pale blue color.
  • WPU Waterborne polyurethane emulsion

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Abstract

提供一种聚氨酯水凝胶的制备方法，所述方法包括：按照质量比1-7:1将脱水的多元醇与多异氰酸酯在氮气气氛下加热到70-90℃反应2-4h；将反应体系降温到40-50℃，加入2,2-二羟甲基丙酸和丙酮反应0.5-1.5h；降温至室温，加入三乙胺，反应10-20min，在高速搅拌下800-1000r/min，滴加水分散，减压蒸馏2h脱丙酮，即可得到水性聚氨酯乳液；将水性聚氨酯乳液与聚乙烯醇溶液按照质量比1-45:10混合，并在-25℃的条件下冷冻8-12h，并在室温条件下解冻4-6h，反复冷冻解冻多次，得到聚氨酯水凝胶。

Description

一种聚氨酯水凝胶的制备方法
本发明属于高分子材料制备技术领域，尤其涉及一种聚氨酯水凝胶的制备方法。
聚氨酯（PU）结构中含有大量重复的氨基甲酸酯链段，其大分子主链是由低聚物多元醇构成的软段和多异氰酸酯与小分子扩链剂构成的硬段嵌段而成的。聚氨酯的大分子链中，由于硬段的极性强，相互间的吸引力大，硬段和软段在热力学上具有自发的发生相分离的倾向。因此，聚氨酯硬段容易聚集在一起，分布于软段相中，形成微相分离结构。正是聚氨酯的这种微相分离的物理特性，使其具有优于其他高分子材料的物理机械性能、抗凝血性、生物相容性等特性。
水凝胶是一类具有三维网状结构、能被水溶胀但却不溶于水的聚合物。其在水中溶胀至平衡体积，仍能保持原有的结构形态。聚氨酯水凝胶兼具聚氨酯和水凝胶的优点，广泛应用于生物医学领域，如：药物缓释载体、角膜接触镜、组织填充材料、创面敷料、医疗传感器等。由于上述聚氨酯和水凝胶的优良特性，聚氨酯水凝胶结合了二者的优良性能，可以应用于多个技术领域。
目前，聚氨酯水凝胶的制备方法均是利用二异氰酸酯与聚乙二醇反应得聚氨酯预聚体后，再和小分子扩链剂或交联剂经聚合、固化后得到聚氨酯弹性体或预聚体，随后在水中或有机溶剂中溶胀形成聚氨酯水凝胶。该类方法的制备过程较为繁琐，且需要加入化学交联剂、有机溶剂或光引发剂等，这些试剂或多或少都有一定毒性对材料本身及外界环境会造成不同程度的污染。
发明内容
本发明提供一种聚氨酯水凝胶的制备方法，旨在解决现有的制备方法过程繁琐，加入的试剂造成污染的问题。
本发明提供一种聚氨酯水凝胶的制备方法，包括：
按照质量比1~7:1将脱水的多元醇与多异氰酸酯加入催化剂并在氮气氛下加热到70~90℃反应2~4h；
将反应体系降温到40~50℃，加入2，2-二羟甲基丙酸并加入丙酮稀释反应0.5~1.5h，其中，所述2，2-二羟甲基丙酸与多元醇的质量比为1:10~20，丙酮的体积与反应体系的体积比为0.1~1:1；
将反应体系降温至室温，加入有机碱液三乙胺，中和10~20min，在高速搅拌下，滴加水分散，减压蒸馏2h脱丙酮，得到水性聚氨酯乳液，其中，三乙胺的质量与2，2-二羟甲基丙酸的摩尔比为1:2~3；
将所述水性聚氨酯乳液与聚乙烯醇溶液按照质量比1~45：10混合，并在-25℃的条件下冷冻8~12h，并在室温下解冻4~6h，反复冷冻解冻多次，得到聚氨酯水凝胶。其中，所述聚乙烯醇溶液的质量分数为12.5%。
本发明提供一种聚氨酯水凝胶的制备方法，本发明通过将制备的水性聚氨酯溶液与聚乙烯醇溶液混合，经过多次冷冻和解冻后得到聚氨酯水凝胶，该制备方法避免使用大量的有机溶剂，化学交联剂，光引发剂不会引起试剂污染。同时，该方法操作简单，条件可控，适合大规模使用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例。
图1是本发明实施例1制备得到的聚氨酯水凝胶的扫描电镜测试图。
具体实施方式
为使得本发明的发明目的、特征、优点能够更加的明显和易懂，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而非全部实施例。基于本发明中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供一种聚氨酯水凝胶的制备方法，该方法主要包括以下步骤：
步骤一、按照质量比1~7:1将脱水的多元醇与多异氰酸酯加入催化剂在氮气气氛下加热到70~90℃反应2~4h；
步骤二、将反应体系降温到40~50℃，加入2，2-二羟甲基丙酸和丙酮反应0.5~1.5h；
其中， 2，2-二羟甲基丙酸与多元醇的质量比为1:10~20，丙酮的体积与反应体系的体积比为0.1~1:1。
步骤三、将反应体系降温至室温，加入有机碱液三乙胺，中和10~20min，高速搅拌，滴加水分散，减压蒸馏2h脱除丙酮，得到水性聚氨酯乳液。
其中，三乙胺的质量与2，2-二羟甲基丙酸的摩尔比为1:2~3。
步骤四、将所述水性聚氨酯溶液与聚乙烯醇溶液按照质量比1~45：10混合，并在-25℃的条件下冷冻8~12h，并在室温下解冻4~6h，反复冷冻解冻多次，得到聚氨酯水凝胶，其中，所述聚乙烯醇溶液的质量分数为12.5%。
本发明提供一种聚氨酯水凝胶的制备方法，本发明通过将制备的水性聚氨酯溶液与聚乙烯醇溶液混合，并经过多次冷冻和解冻最终得到聚氨酯水凝胶，该制备方法避免使用大量的有机溶剂，化学交联剂，光引发剂不会引起试剂污染。同时，该方法操作简单，条件可控，适合大规模使用。
具体地，步骤一中的多元醇为蓖麻油基二元醇、聚醚二元醇、聚已内酯乙二醇、聚乙二醇和聚四氢呋喃醚二醇中的至少一种，多异氰酸酯包括4，4’-二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯中的至少一种。
在实际应用中，可在100℃的条件下对多元醇进行真空脱水，并将多元醇与与多异氰酸酯装入有搅拌器、冷凝回流管和氮气的三口烧瓶中进行加热反应。
优选地，加热温度为70℃，反应时间为3h，此时，反应体系中-NCO的含量为10%。
具体地，步骤二中，当反应体系中-NCO的含量为10%，利用冰水降温到50℃，加丙酮后可以降低体系的粘度。
具体地，步骤三中，将反应体系降温至室温，加入三乙胺，中和体系中的羧基官能团。并在800~1000r/min高速搅拌下，缓慢滴加去离子水进行分散。将得到的溶液置于旋转蒸发仪中，在温度为45~55℃，压强为0.08~0.1MPa的条件下，减压蒸馏2h，当丙酮含量为0.5%时，得到水性聚氨酯乳液。
具体地，步骤四中，将100g的聚乙烯醇加入到烧瓶中，加入700mL的蒸馏水，在90℃的水浴中反应3~4小时至PVA完全溶解，制得澄清透明质量分数为12.5%的PVA水溶液。在水性聚氨酯乳液中缓慢滴加PVA溶液，其中，二者的质量比为1~45：10。优选为1：1。将混合液置于-25℃冷冻8~12小时后，然后在25℃下解冻4~8小时，往复如此冷冻解冻3~5次，最后一次解冻后，置于冷冻干燥机上冷冻干燥至少24h以上，直至凝胶中的水分被完全抽干，得到聚氨酯多孔材料。该材料为多孔复合型高吸液材料，机械性能、无毒生物相容性能优良且抗撕裂。
实施例1
1、水性聚氨酯乳液WPU的制备
称取22.4g 聚醚二元醇（分子量4800）于三口烧瓶中通氮气，加热到100℃，抽真空除水2h后，加入5.25g 4，4’-二苯基甲烷二异氰酸酯（MDI）、0.12g三乙烯二胺催化剂，在70℃的条件下反应2h，得到聚氨酯预聚物。
将聚氨酯预聚物降温至50℃，加入1.25g 2,2-二羟甲基丙酸（DMPA）和40mL的丙酮降低体系黏度，反应2h。反应完成后，降温至室温，加入0.75g三乙胺，中和反应15min，。最后在1000r/min高速搅拌下，缓慢滴加去离子水进行分散，置于旋转蒸发仪中，在45℃和0.09MPa的条件下减压蒸馏2h，至丙酮含量为0.5%，得到乳白色水性聚氨酯乳液（WPU）。
2、聚氨酯水凝胶的制备
称量100g的聚乙烯醇加入到烧瓶中，加入700mL的蒸馏水，在90℃的水浴中加热4小时至PVA完全溶解，制得澄清透明12.5%PVA水溶液。
将制得的WPU乳液称取1.2g于烧杯中，利用高速磁力搅拌，并向其中缓缓加入10g PVA水溶液，30min后，得到搅拌均匀混合液。将混合液注入24孔板的模具中，并在-25℃的条件下冷冻12小时，以及在室温下解冻6小时，按照上述条件重复冷冻解冻5次。第5次解冻后在-25℃的条件下冷冻5小时至凝胶内的流动水完全凝固，再置于冷冻干燥机冷冻干燥48小时，直至凝胶中的水分完全被抽干，得到干的聚氨酯水凝胶材料。
如图1所示，图1为实施例1制备得到的聚氨酯水凝胶材料的扫描电镜测试图，其中，由图可以看出，该材料表面为多孔结构。
实施例2
1、水性聚氨酯乳液WPU的制备
称取10.3g 蓖麻油基二元醇（分子量300）于三口烧瓶中，加热到100℃，抽真空除水2h后，加入12.5g 4，4’-二苯基甲烷二异氰酸酯（MDI）、0.08g三乙烯二胺催化剂，在70℃的条件下反应2h，得到聚氨酯预聚物。
将聚氨酯预聚物降温至50℃，加入2.3g 2,2-二羟甲基丙酸（DMPA）和30mL的丙酮降低体系黏度，反应2h。反应完成后，降温至室温，加入1.25g三乙胺，中和反应15min。最后在800r/min高速搅拌下，缓慢滴加去离子水进行分散，置于旋转蒸发仪中，在45℃和0.09MPa的条件下减压蒸馏2h，至丙酮含量为0.5%，得到淡蓝色水性聚氨酯乳液（WPU）。
2、聚氨酯水凝胶的制备
称量100g的聚乙烯醇加入到烧瓶中，加入700mL的蒸馏水，在90℃的水浴中加热4小时至PVA完全溶解，制得澄清透明12.5%PVA水溶液。
将制得的WPU乳液称取4.6g于烧杯中，利用高速磁力搅拌，并向其中缓缓加入10g PVA水溶液，30min后，得到搅拌均匀混合液。将混合液注入24孔板的模具中，并在-20℃的条件下冷冻12小时，以及在室温下解冻6小时，按照上述条件重复冷冻解冻5次。第5次解冻后在-25℃的条件下冷冻5小时至凝胶内的流动水完全凝固，再置于冷冻干燥机冷冻干燥48小时，直至凝胶中的水分完全被抽干，得到干的聚氨酯水凝胶材料。
实施例3
1、水性聚氨酯乳液WPU的制备
称取30g 聚已内酯乙二醇（分子量2000）于三口烧瓶中，加热到100℃，抽真空除水2h后，加入7.2g 4，4’-二苯基甲烷二异氰酸酯（MDI）、0.08g三乙烯二胺催化剂，在70℃的条件下反应2h，得到聚氨酯预聚物。
将聚氨酯预聚物降温至50℃，加入1.5g 2,2-二羟甲基丙酸（DMPA）和40mL的丙酮降低体系黏度，反应2h。反应完成后，降温至室温，加入1.2g三乙胺，中和反应15min。最后在1000r/min高速搅拌下，缓慢滴加去离子水进行分散，置于旋转蒸发仪中，在45℃和0.09MPa的条件下减压蒸馏2h，至丙酮含量为0.5%，得到白色水性聚氨酯乳液（WPU）。
2、聚氨酯水凝胶的制备
称量100g的聚乙烯醇加入到烧瓶中，加入700mL的蒸馏水，在90℃的水浴中加热4小时至PVA完全溶解，制得澄清透明12.5%PVA水溶液。
将制得的WPU乳液称取10.8g于烧杯中，利用高速磁力搅拌，并向其中缓缓加入10g PVA水溶液，30min后，得到搅拌均匀混合液。将混合液注入24孔板的模具中，并在-25℃的条件下冷冻12小时，以及在室温下解冻6小时，按照上述条件重复冷冻解冻5次。第5次解冻后在-25℃的条件下冷冻5小时至凝胶内的流动水完全凝固，再置于冷冻干燥机冷冻干燥48小时，直至凝胶中的水分完全被抽干，得到干的聚氨酯水凝胶材料。
实施例4
1、水性聚氨酯乳液WPU的制备
称取10g 聚乙二醇（分子量1000）于三口烧瓶中，加热到100℃，抽真空除水2h后，加入1.5g六亚甲基二异氰酸酯（HDI）、0.1g三乙烯二胺催化剂，在70℃的条件下反应2h，得到聚氨酯预聚物。
将聚氨酯预聚物降温至50℃，加入1.3g 2,2-二羟甲基丙酸（DMPA）和30mL的丙酮降低体系黏度，反应2h。反应完成后，降温至室温，加入0.5g三乙胺，中和反应15min。最后在800r/min高速搅拌下，缓慢滴加去离子水进行分散，置于旋转蒸发仪中，在45℃和0.09MPa的条件下减压蒸馏2h，至丙酮含量为0.5%，得到白色水性聚氨酯乳液（WPU）。
2、聚氨酯水凝胶的制备
称量100g的聚乙烯醇加入到烧瓶中，加入700mL的蒸馏水，在90℃的水浴中加热4小时至PVA完全溶解，制得澄清透明12.5%PVA水溶液。
将制得的WPU乳液称取25.2g于烧杯中，利用高速磁力搅拌，并向其中缓缓加入10g PVA水溶液，30min后，得到搅拌均匀混合液。将混合液注入24孔板的模具中，并在-25℃的条件下冷冻12小时，以及在室温下解冻6小时，按照上述条件重复冷冻解冻5次。第5次解冻后在-25℃的条件下冷冻5小时至凝胶内的流动水完全凝固，再置于冷冻干燥机冷冻干燥48小时，直至凝胶中的水分完全被抽干，得到干的聚氨酯水凝胶材料。
实施例5
1、水性聚氨酯乳液WPU的制备
称取15g 聚四氢呋喃醚二醇（分子量1000）于三口烧瓶中，加热到100℃，抽真空除水2h后，加入3.25g异佛尔酮二异氰酸酯（IPDI）、0.04g三乙烯二胺催化剂，在70℃的条件下反应2h，得到聚氨酯预聚物。
将聚氨酯预聚物降温至50℃，加入0.75g 2,2-二羟甲基丙酸（DMPA）和40mL的丙酮稀释反应体系，反应2h。反应完成后，降温至室温，加入0.45g三乙胺，中和反应15min。最后在1000r/min高速搅拌下，缓慢滴加去离子水进行分散，置于旋转蒸发仪中，在45℃和0.09MPa的条件下减压蒸馏2h，至丙酮含量为0.5%，得到淡蓝色水性聚氨酯乳液（WPU）。
2、聚氨酯水凝胶的制备
称量100g的聚乙烯醇加入到烧瓶中，加入700mL的蒸馏水，在90℃的水浴中加热4小时至PVA完全溶解，制得澄清透明12.5%PVA水溶液。
将制得的WPU乳液称取43.2g于烧杯中，利用高速磁力搅拌，并向其中缓缓加入10g PVA水溶液，30min后，得到搅拌均匀混合液。将混合液注入24孔板的模具中，并在-25℃的条件下冷冻12小时，以及在室温下解冻6小时，按照上述条件重复冷冻解冻5次。第5次解冻后在-25℃的条件下冷冻5小时至凝胶内的流动水完全凝固，再置于冷冻干燥机冷冻干燥48小时，直至凝胶中的水分完全被抽干，得到干的聚氨酯水凝胶材料。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (6)

  1. 一种聚氨酯水凝胶的制备方法，其特征在于，所述方法包括：
    按照质量比1~7:1将脱水的多元醇与多异氰酸酯加入催化剂并在氮气氛下加热到70~90℃反应2~4h；
    将反应体系降温到40~50℃，加入2，2-二羟甲基丙酸并加入丙酮稀释反应0.5~1.5h，其中，2，2-二羟甲基丙酸与多元醇的质量比为1:10~20，丙酮的体积与反应体系的体积比为0.1~1:1；
    将反应体系降温至室温，加入有机碱液三乙胺，中和10~20min，在高速搅拌下，滴加水分散，减压蒸馏2h脱丙酮，得到水性聚氨酯乳液，其中，三乙胺的质量与2，2-二羟甲基丙酸的摩尔比为1:2~3；
    将所述水性聚氨酯乳液与聚乙烯醇溶液按照质量比1~45：10混合，并在-25℃的条件下冷冻8~12h，并在室温下解冻4~6h，反复冷冻解冻多次，得到聚氨酯水凝胶。其中，所述聚乙烯醇溶液的质量分数为12.5%。
  2. 根据权利要求1所述的方法，其特征在于，所述多元醇为蓖麻油基二元醇、聚醚二元醇、聚已内酯乙二醇、聚乙二醇和聚四氢呋喃醚二醇中的至少一种。
  3. 根据权利要求1所述的方法，其特征在于，所述多异氰酸酯包括4，4’-二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯中的至少一种。
  4. 根据权利要求1所述的方法，其特征在于，冷冻解冻的次数为3~5次。
  5. 根据权利要求1所述的方法，其特征在于，所述减压蒸馏的条件为：温度为45~55℃，压强为0.08~0.1MPa。
  6. 根据权利要求1所述的方法，其特征在于，搅拌的速率为800~1000r/min。
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