技术领域technical field
本发明涉及吸湿凝胶开发技术领域，具体涉及一种光热吸湿聚合物凝胶及其制备方法与应用。The invention relates to the technical field of hygroscopic gel development, in particular to a photothermal hygroscopic polymer gel and its preparation method and application.
背景技术Background technique
湿气是一种无处不在的自然现象，通过水蒸气的形式存在于大气中，约占全球水资源的10％。而湿气作为一种重要的资源，在人们的日常生产生活中发挥着重要的作用。对于偏远的内陆地区和干旱地区，利用湿气生产淡水资源能够有效解决当地水资源短缺的问题。同时，人们利用湿气还可以实现电池发电、空间制冷等方面的应用。但湿气含量过高也会造成一定的危害，如会导致金属腐蚀、加重空气污染程度、影响农作物的生长等，因此需要对湿气进行管理。Humidity is a ubiquitous natural phenomenon that exists in the atmosphere in the form of water vapor, accounting for about 10% of global water resources. As an important resource, moisture plays an important role in people's daily production and life. For remote inland areas and arid areas, the use of moisture to produce fresh water resources can effectively solve the problem of local water shortage. At the same time, people can use moisture to realize applications such as battery power generation and space cooling. However, excessive moisture content can also cause certain hazards, such as causing metal corrosion, aggravating air pollution, and affecting the growth of crops, etc. Therefore, moisture management is required.
近年来开发了一系列吸湿材料来管理湿气，其中最广泛使用的是多孔基质，如硅胶、碳纳米球、金属有机框架(MOFs)等。授权公告号为CN 216849573 U的实用新型专利公开了一种免更换吸湿硅胶的变压器呼吸器，该呼吸器通过内置吸湿硅胶实现对湿气的富集并通过热风对吸湿硅胶进行烘干，但吸湿硅胶的容量小，吸湿速率较慢。A series of hygroscopic materials have been developed in recent years to manage moisture, among which the most widely used are porous substrates, such as silica gel, carbon nanospheres, metal-organic frameworks (MOFs), etc. The utility model patent with the authorized notification number CN 216849573 U discloses a transformer respirator that does not need to replace the hygroscopic silica gel. Silica gel has a small capacity and a slow moisture absorption rate.
公开号为CN 112146216 A的发明专利申请公开了一种温湿度独立的空调系统及其控制方法，所述的温湿度独立的空调系统中通过金属有机框架(MOFs)的吸湿-再生-吸湿实现对湿度的有效调整，但金属有机框架吸湿能力较弱，成本高，制备工艺复杂，并且这些多孔基质与水分子之间的结合力较强，导致较慢的吸湿动力学和脱湿动力学，严重影响了多孔基质材料在空气制水方面的应用。The invention patent application with the publication number CN 112146216 A discloses a temperature-humidity independent air-conditioning system and its control method. Effective adjustment of humidity, but metal-organic frameworks have weak moisture absorption capacity, high cost, complicated preparation process, and the strong binding force between these porous substrates and water molecules, resulting in slower moisture absorption kinetics and dehydration kinetics, seriously It affects the application of porous matrix materials in air water production.
水凝胶复合材料具有制备简单、成本低、容量大、吸湿能力强等优点。水凝胶通过聚合物网络的快速膨胀促进对水分的吸附，并将吸附的水液化储存到凝胶网络中防止其泄露，在光照或加热的条件下将水分脱除，得到纯净水。Hydrogel composites have the advantages of simple preparation, low cost, large capacity, and strong moisture absorption capacity. The hydrogel promotes the adsorption of water through the rapid expansion of the polymer network, liquefies and stores the adsorbed water into the gel network to prevent its leakage, and removes the water under the condition of light or heating to obtain pure water.
聚合物凝胶日制水量的多少取决于凝胶的吸湿动力学和脱湿动力学的速率，而聚合物凝胶吸湿动力学速率是由水分子在凝胶中的传质速率决定的，由于一般凝胶的孔径较小，导致传质困难，因此，吸湿聚合物凝胶通常具有较慢的吸湿动力学速率。此外，由于聚合物凝胶中吸湿盐的存在，吸湿盐与水分子之间具有强相互作用力，导致吸湿凝胶脱附过程严重受到吸湿盐高解吸热的影响，导致吸湿聚合物凝胶的具有较慢的脱湿动力学速率。The daily water production of polymer gel depends on the rate of hydroscopic kinetics and dehydration kinetics of the gel, while the kinetic rate of polymer gel hygroscopicity is determined by the mass transfer rate of water molecules in the gel, because Generally, the pore size of the gel is small, resulting in difficulty in mass transfer. Therefore, the hygroscopic polymer gel usually has a slow hygroscopic kinetic rate. In addition, due to the presence of hygroscopic salts in polymer gels, there is a strong interaction between hygroscopic salts and water molecules, resulting in the desorption process of hygroscopic gels being severely affected by the high desorption heat of hygroscopic salts, resulting in the desorption of hygroscopic polymer gels. have a slower rate of dehumidification kinetics.
公开号为CN 111032208 A的发明专利申请公开了一种吸湿性水凝胶，所述水凝胶能够显著降低水的解吸热，加快凝胶脱湿，但该凝胶吸湿能力和吸湿速率较差，难以实现快速制水。The invention patent application with the publication number CN 111032208 A discloses a hygroscopic hydrogel, which can significantly reduce the desorption heat of water and accelerate dehumidification of the gel, but the hygroscopic capacity and rate of the gel are relatively low. Poor, it is difficult to achieve rapid water production.
公开号为CN 113385152 A的发明专利申请公开了一种凝胶干燥剂颗粒及其制备方法。所述凝胶干燥剂具有价格低廉、高再生性的特点，但该凝胶干燥剂吸湿能力较差且制备过程复杂，日产水量低。The invention patent application with publication number CN 113385152 A discloses a gel desiccant particle and a preparation method thereof. The gel desiccant has the characteristics of low price and high reproducibility, but the gel desiccant has poor hygroscopicity, complicated preparation process and low daily water production.
公开号为CN 114940799 A的发明专利申请公开了一种用于环境水收集的核壳结构PAA-PNIPAAm水凝胶材料制备方法，所述水凝胶具有优异的吸湿性和脱湿性，但该凝胶吸湿速率和脱湿速率较差，难以实现快速制水，且制备过程复杂难以大规模生产。The invention patent application with publication number CN 114940799 A discloses a method for preparing a PAA-PNIPAAm hydrogel material with a core-shell structure for environmental water collection. The hydrogel has excellent hygroscopicity and dehumidification, but the gel The moisture absorption rate and dehumidification rate of glue are poor, it is difficult to achieve rapid water production, and the preparation process is complicated and difficult to produce on a large scale.
鉴于上述现有技术，如何同时提高吸湿聚合物凝胶的吸湿/脱湿动力学速率是提高空气制水日产水量的关键因素。因此，寻找一种技术方案来制备具有高的吸湿/脱湿动力学速率的聚合物凝胶以实现湿气的有效利用，对解决部分地区水资源的短缺以及湿气含量过高造成的危害具有重要的意义。In view of the above-mentioned prior art, how to increase the kinetic rate of moisture absorption/dehydration of the hygroscopic polymer gel at the same time is a key factor for increasing the daily water production of air-based water production. Therefore, finding a technical solution to prepare a polymer gel with a high moisture absorption/dehydration kinetic rate to realize the effective utilization of moisture is of great significance for solving the shortage of water resources in some areas and the harm caused by excessive moisture content. Significance.
发明内容Contents of the invention
鉴于上述现有技术的不足，本发明提供了一种光热吸湿聚合物凝胶的制备方法，包括前驱液的制备、冰模板法制备凝胶样品以及吸湿性无机盐掺杂，本发明方法制备得到的光热吸湿聚合物凝胶具有互联大孔结构，制备工艺简单，原材料来源广，成本低，制备过程中无需昂贵的制备仪器，具有较好的规模化制备应用前景。In view of the above-mentioned deficiencies in the prior art, the present invention provides a method for preparing a photothermal hygroscopic polymer gel, including the preparation of the precursor solution, the preparation of the gel sample by the ice template method, and the doping of hygroscopic inorganic salts. The preparation method of the present invention The obtained photothermal moisture-absorbing polymer gel has an interconnected macroporous structure, simple preparation process, wide source of raw materials, low cost, no need for expensive preparation instruments in the preparation process, and has good application prospects for large-scale preparation.
一种光热吸湿聚合物凝胶的制备方法，其特征在于，包括以下步骤：A method for preparing a photothermal moisture-absorbing polymer gel, comprising the following steps:
(1)将引发剂、交联剂溶于聚合物单体溶液中，再加入具有光热转换性能的材料，搅拌均匀，随后加入四甲基乙二胺，得到前驱液；(1) Dissolving the initiator and cross-linking agent in the polymer monomer solution, then adding materials with light-to-heat conversion properties, stirring evenly, and then adding tetramethylethylenediamine to obtain a precursor solution;
(2)采用冰模板法制备凝胶样品，所述冰模板法制备凝胶样品的步骤为：将前驱液注入模具中，密封进行预冻后，进行聚合；(2) Prepare the gel sample by the ice template method, the step of preparing the gel sample by the ice template method is: inject the precursor solution into the mold, seal and pre-freeze, and then polymerize;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，除去未反应的单体和交联剂，烘干；(3) Soak the gel sample obtained in step (2) in deionized water, remove unreacted monomers and crosslinking agents, and dry;
(4)将步骤(3)中得到的产物浸泡在吸湿性无机盐溶液中进行掺杂，烘干，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a hygroscopic inorganic salt solution for doping, and dry to obtain a photothermal hygroscopic polymer gel.
本发明利用冰模板的方法制备光热吸湿聚合物凝胶，通过预冻过程中冰晶的生长，占据溶液体系中的位置，形成大孔结构，将预冻后的样品在低温下进行聚合，在聚合的过程中大孔结构被保留下来，从而获得具有互联大孔结构的聚合物凝胶。由于大孔结构的存在显著加快了水分子的传质，使得所制备的聚合物凝胶具有优异的吸湿动力学性能。此外，由于聚合物凝胶中自由水和中间水含量较高，其在全波段范围内都具有强的光谱吸收率，使得所制备得到的聚合物凝胶具有优异的脱湿动力学性能，能在全湿度范围内实现快速的水分收集、脱附和再生。The invention utilizes the method of ice template to prepare photothermal moisture-absorbing polymer gel, and through the growth of ice crystals in the pre-freezing process, it occupies the position in the solution system to form a macroporous structure, and the pre-frozen samples are polymerized at low temperature. During the polymerization process, the macroporous structure is preserved, thereby obtaining a polymer gel with an interconnected macroporous structure. Due to the existence of the macroporous structure, the mass transfer of water molecules is significantly accelerated, so that the prepared polymer gel has excellent hygroscopic kinetic properties. In addition, due to the high content of free water and intermediate water in the polymer gel, it has a strong spectral absorption rate in the whole band range, so that the prepared polymer gel has excellent dehydration kinetics, and can Rapid moisture collection, desorption and regeneration over the full humidity range.
优选地，步骤(1)中，所述的引发剂为过硫酸铵、过硫酸钾、过硫酸钠中的一种，或者为硫代硫酸钠和过硫酸钾、亚硫酸氢钠和过硫酸铵、亚硫酸氢钾和过硫酸铵、亚硫酸钠和过硫酸钾、亚硫酸铵和过硫酸钾中的一种。Preferably, in step (1), the initiator is one of ammonium persulfate, potassium persulfate, sodium persulfate, or sodium thiosulfate and potassium persulfate, sodium bisulfite and ammonium persulfate , one of potassium bisulfite and ammonium persulfate, sodium sulfite and potassium persulfate, ammonium sulfite and potassium persulfate.
优选地，步骤(1)中，所述的前驱液中引发剂的含量为0.08～0.74wt％。Preferably, in step (1), the content of the initiator in the precursor solution is 0.08-0.74wt%.
由于过硫酸铵成本低，反应条件温和，能在低温下引发聚合反应，更优选地，所述的引发剂为过硫酸铵。Due to the low cost of ammonium persulfate and mild reaction conditions, the polymerization reaction can be initiated at low temperature. More preferably, the initiator is ammonium persulfate.
优选地，所述的前驱液中过硫酸铵的含量为0.12～0.49wt％。Preferably, the content of ammonium persulfate in the precursor solution is 0.12-0.49wt%.
优选地，步骤(1)中，所述的交联剂为N,N-亚甲基双丙烯酰胺、乙二醇二甲基丙烯酸酯、二乙烯基苯、二异氰酸酯或三烯丙基异三聚氰酸酯中的一种。Preferably, in step (1), the crosslinking agent is N,N-methylenebisacrylamide, ethylene glycol dimethacrylate, divinylbenzene, diisocyanate or triallyl isotri A kind of polycyanate.
优选地，步骤(1)中，所述的前驱液中交联剂的含量为0.03～0.42wt％。Preferably, in step (1), the content of the crosslinking agent in the precursor solution is 0.03-0.42wt%.
由于N,N-亚甲基双丙烯酰胺成本低，在水溶液中易于分散，更优选地，所述的交联剂为N,N-亚甲基双丙烯酰胺。Since N,N-methylenebisacrylamide has low cost and is easy to disperse in aqueous solution, more preferably, the crosslinking agent is N,N-methylenebisacrylamide.
优选地，所述的前驱液中N,N-亚甲基双丙烯酰胺的含量为0.05～0.35wt％。Preferably, the content of N,N-methylenebisacrylamide in the precursor solution is 0.05-0.35wt%.
优选地，步骤(1)中，所述的聚合物单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵、丙烯酸钠及其衍生物、丙烯酰胺、N-异丙基丙烯酰胺、甲基丙烯酸羟乙酯、丙烯酰氧乙基三甲基氯化铵中的任意一种或两种以上的组合。Preferably, in step (1), the polymer monomer is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, sodium acrylate and Any one or a combination of two or more of its derivatives, acrylamide, N-isopropylacrylamide, hydroxyethyl methacrylate, and acryloyloxyethyltrimethylammonium chloride.
优选地，所述的前驱液中聚合物单体的含量为4.3～48.7wt％。Preferably, the content of the polymer monomer in the precursor solution is 4.3-48.7wt%.
由于[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵具有“反电解质效应”，聚合物在盐溶液中具有更高的溶胀度，从而提高了吸湿性无机盐的负载量，进而提高聚合物凝胶的吸湿性能。更优选地，所述的聚合物单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵。Due to the "anti-electrolyte effect" of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonate propyl)ammonium hydroxide, the polymer has a higher degree of swelling in salt solution, Therefore, the loading capacity of the hygroscopic inorganic salt is increased, and the hygroscopic performance of the polymer gel is further improved. More preferably, the polymer monomer is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide.
优选地，所述的前驱液中[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵的含量为7.4～36.8wt％。Preferably, the content of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide in the precursor solution is 7.4-36.8wt%.
优选地，步骤(1)中，所述的具有光热转换性能的材料为石墨烯、氧化石墨烯、碳纳米管、聚吡咯、吲哚菁绿、石墨、炭黑、无定形碳、金属氧硫族化合物、黑钛类化合物、铝纳米颗粒中的任意一种或两种以上的组合。Preferably, in step (1), the material with light-to-heat conversion performance is graphene, graphene oxide, carbon nanotubes, polypyrrole, indocyanine green, graphite, carbon black, amorphous carbon, metal oxide Any one or a combination of two or more of chalcogenide compounds, black titanium compounds, and aluminum nanoparticles.
优选地，步骤(1)中，所述的前驱液中具有光热转换性能的材料的含量为1.2～8.1wt％。Preferably, in step (1), the content of the material with light-to-heat conversion performance in the precursor solution is 1.2-8.1 wt%.
由于氧化石墨烯成本低、在水溶液中易于分散，更优选地，所述的具有光热转换性能的材料为氧化石墨烯。Since graphene oxide is low in cost and easy to disperse in aqueous solution, more preferably, the material with light-to-heat conversion performance is graphene oxide.
优选地，所述的前驱液中氧化石墨烯的含量为1.4～6.9wt％。Preferably, the content of graphene oxide in the precursor solution is 1.4-6.9 wt%.
优选地，步骤(1)中，所述的前驱液中四甲基乙二胺的含量为0.15～0.61wt％。Preferably, in step (1), the content of tetramethylethylenediamine in the precursor solution is 0.15-0.61wt%.
优选地，步骤(2)中，所述的预冻温度为-10～-100℃，时间为0.5～2.5h。Preferably, in step (2), the prefreezing temperature is -10 to -100° C., and the time is 0.5 to 2.5 hours.
优选地，步骤(2)中，所述的聚合反应温度为-25～4℃，时间为6～48h。Preferably, in step (2), the polymerization reaction temperature is -25-4° C., and the time is 6-48 hours.
优选地，步骤(2)中，所述的凝胶样品的孔径为0.3～1.5mm。Preferably, in step (2), the pore diameter of the gel sample is 0.3-1.5 mm.
优选地，步骤(3)中，所述的浸泡温度为10～40℃，时间为4～36h。Preferably, in step (3), the soaking temperature is 10-40° C., and the soaking time is 4-36 hours.
优选地，步骤(3)中，所述的烘干温度为50～90℃，时间为3～16h。Preferably, in step (3), the drying temperature is 50-90° C., and the drying time is 3-16 hours.
步骤(4)中，所述的吸湿性无机盐溶液中的无机盐离子作为凝聚核，可使空气聚集，达到空气制水的目的。In step (4), the inorganic salt ions in the hygroscopic inorganic salt solution serve as condensation nuclei to allow air to gather to achieve the purpose of producing water from air.
优选地，步骤(4)中，所述的吸湿性无机盐溶液为氯化锂、氯化钙、氯化铁、硝酸铵、硫酸铵、硫酸铁、氯化铁、溴化铁或硝酸钾的水溶液。Preferably, in step (4), the hygroscopic inorganic salt solution is lithium chloride, calcium chloride, ferric chloride, ammonium nitrate, ammonium sulfate, ferric sulfate, ferric chloride, ferric bromide or potassium nitrate aqueous solution.
优选地，步骤(4)中，所述的吸湿性无机盐溶液的浓度为2.91～57.6wt％。Preferably, in step (4), the concentration of the hygroscopic inorganic salt solution is 2.91-57.6 wt%.
由于氯化锂吸湿速率快，效果好，适用湿度范围广，更优选地，所述的吸湿性无机盐溶液为氯化锂的水溶液。Due to the fast moisture absorption rate of lithium chloride, good effect and wide range of applicable humidity, more preferably, the hygroscopic inorganic salt solution is an aqueous solution of lithium chloride.
优选地，步骤(4)中，所述的氯化锂的水溶液的浓度为4.58～37.5wt％。Preferably, in step (4), the concentration of the lithium chloride aqueous solution is 4.58-37.5 wt%.
优选地，步骤(4)中，所述的掺杂温度为10～40℃，时间为0.5～64h。Preferably, in step (4), the doping temperature is 10-40°C, and the time is 0.5-64h.
优选地，步骤(4)中，所述的烘干温度为70～130℃，时间为12～48h。Preferably, in step (4), the drying temperature is 70-130° C., and the drying time is 12-48 hours.
本发明还提供了一种由上述制备方法制备得到的光热吸湿聚合物凝胶，所述的光热吸湿聚合物凝胶为包含光热转换效应和吸湿性能材料的聚合物凝胶。该光热吸湿聚合物凝胶同时具有优异的光热转化性能和吸湿/脱湿动力学性能，能在宽温度范围(15℃～35℃)、全湿度范围内实现快速的水分收集、脱附和再生。The present invention also provides a photothermal moisture-absorbing polymer gel prepared by the above preparation method. The photothermal moisture-absorbing polymer gel is a polymer gel containing materials with photothermal conversion effect and hygroscopic performance. The photothermal moisture-absorbing polymer gel has excellent photothermal conversion performance and moisture absorption/dehydration kinetics at the same time, and can realize rapid moisture collection, desorption and regeneration.
优选地，所述的光热吸湿聚合物凝胶具有0.3～1.5mm的大孔互联结构。Preferably, the photothermal hygroscopic polymer gel has a macroporous interconnection structure of 0.3-1.5 mm.
本发明还提供了一种所述的光热吸湿聚合物凝胶在空气制水、空间除湿、空间蒸发辐射制冷和电池湿气发电领域中的应用。本发明制备的光热吸湿聚合物凝胶具有快速的吸湿动力学速率和脱湿动力学速率，且气候适应性强，应用范围广。The invention also provides an application of the photothermal hygroscopic polymer gel in the fields of water production from air, space dehumidification, space evaporative radiation cooling and battery moisture power generation. The photothermal moisture-absorbing polymer gel prepared by the invention has fast moisture absorption kinetic rate and dehydration kinetic rate, and has strong climate adaptability and wide application range.
在没有光照的条件下，光热吸湿聚合物凝胶中掺杂的吸湿性无机盐能够对空气中的水蒸气进行吸附，液化，储存在凝胶内部；在有光照的条件下，通过光热吸湿聚合物凝胶的光热转换效应，将吸附的水进行蒸发收集，从而得到纯净水。所制备的水中的钠、钾、镁、钙四种离子的含量符合WHO的饮用水的标准。In the absence of light, the hygroscopic inorganic salt doped in the photothermal hygroscopic polymer gel can absorb water vapor in the air, liquefy it, and store it inside the gel; The light-to-heat conversion effect of the hygroscopic polymer gel evaporates and collects the adsorbed water to obtain pure water. The contents of four ions of sodium, potassium, magnesium and calcium in the prepared water meet the drinking water standard of WHO.
本发明的光热吸湿聚合物凝胶在较低的湿度下也能实现空气制水，且整个过程无需外界任何能量输入，而且同时具备较快的吸湿动力学和脱湿动力学速率，能够在一天之内实现多个吸湿-脱湿的循环，具有更高的日产水量，在空气制水领域有较好的应用前景。The photothermal moisture-absorbing polymer gel of the present invention can also realize air-to-water production at relatively low humidity, and the whole process does not require any external energy input, and at the same time has relatively fast moisture absorption kinetics and dehumidification kinetics rates, and can be used in It realizes multiple moisture absorption-dehumidification cycles within a day, has a higher daily water production, and has a good application prospect in the field of air water production.
本发明的光热吸湿聚合物凝胶具有优异的吸湿量和吸湿速率，能够实现对密闭环境的快速除湿，从而降低高湿度带来的危害，在空间除湿领域应用前景广阔。The photothermal moisture-absorbing polymer gel of the present invention has excellent moisture absorption capacity and moisture absorption rate, can realize rapid dehumidification of a closed environment, thereby reducing the harm caused by high humidity, and has broad application prospects in the field of space dehumidification.
与现有技术相比，本发明的有益效果在于：Compared with prior art, the beneficial effect of the present invention is:
(1)本发明采用冰模板法制备具有互联大孔结构的光热吸湿聚合物凝胶，该方法制备工艺简单，原材料来源广，成本低，制备过程中无需昂贵的制备仪器，具有较好的规模化制备应用前景。(1) The present invention adopts the ice template method to prepare the photothermal moisture-absorbing polymer gel with interconnected macroporous structure. The method has simple preparation process, wide source of raw materials, low cost, no expensive preparation equipment in the preparation process, and has better Application prospect of large-scale preparation.
(2)本发明制备的光热吸湿聚合物凝胶为包含光热转换效应和吸湿性能材料的聚合物凝胶，该光热吸湿聚合物凝胶同时具有优异的光热转化性能和吸湿/脱湿动力学性能，能在宽温度范围(15℃～35℃)、全湿度范围内实现快速的水分收集、脱附和再生。(2) The photothermal moisture-absorbing polymer gel prepared by the present invention is a polymer gel containing materials with photothermal conversion effect and hygroscopic performance, and the photothermal moisture-absorbing polymer gel has excellent photothermal conversion performance and moisture absorption/desorption Wet dynamic performance, can realize rapid water collection, desorption and regeneration in a wide temperature range (15°C ~ 35°C) and full humidity range.
(3)本发明制备的光热吸湿聚合物凝胶具有快速的吸湿动力学速率和脱湿动力学速率，且气候适应性强，应用范围广，在空气制水、空间除湿、空间蒸发辐射制冷和电池湿气发电等领域具有较好的应用前景。(3) The photothermal moisture-absorbing polymer gel prepared by the present invention has a fast moisture absorption kinetic rate and dehumidification kinetic rate, and has strong climate adaptability and a wide range of applications. It has a good application prospect in fields such as battery moisture power generation.
(4)本发明制备的光热吸湿聚合物凝胶的吸湿/脱湿速率快，能够实现快速的空气制水，提高日产水量，整个过程无需任何外界能量的输入，循环性能好。采用本发明的光热吸湿聚合物凝胶制水，日产水量可达3.36～20.86g g-1day-1，是室温聚合方法制备的光热吸湿聚合物凝胶的1.5倍以上，且所制备得到的水中的钠、钾、镁、钙四种离子的含量符合WHO饮用水的标准。(4) The photothermal moisture-absorbing polymer gel prepared by the present invention has a fast moisture absorption/dehumidification rate, can realize rapid air water production, and increase daily water production. The whole process does not require any external energy input, and the cycle performance is good. Using the photothermal moisture-absorbing polymer gel of the present invention to produce water, the daily water production can reach 3.36-20.86gg-1 day-1 , which is more than 1.5 times that of the photothermal moisture-absorbing polymer gel prepared by the room temperature polymerization method, and the prepared The content of sodium, potassium, magnesium and calcium in the water meets the WHO drinking water standard.
(5)本发明制备的光热吸湿聚合物凝胶具有优异的吸湿量和吸湿速率，在无光照条件下，吸附速率系数可达2.478*10-4s-1～3.384*10-4s-1，吸湿量可达0.7～4.9g g-1，2h内可达到平衡吸湿量的80％；光照条件下，脱湿速率可达2.4～7g g-1h-1，40min内可脱除80％的水分，脱湿速率可达2.4～7g g-1h-1，能够实现对密闭环境的快速除湿，从而降低高湿度带来的危害，在空间除湿领域具有较好的应用前景。(5) The photothermal hygroscopic polymer gel prepared by the present invention has excellent moisture absorption capacity and moisture absorption rate, and the adsorption rate coefficient can reach 2.478*10-4 s-1 ~ 3.384*10-4 s-1 under the condition of no light1. The moisture absorption can reach 0.7～4.9gg-1 , and 80% of the equilibrium moisture absorption can be achieved within 2 hours; under light conditions, the dehumidification rate can reach 2.4～7g g-1 h-1 , and 80% can be removed within 40 minutes The dehumidification rate can reach 2.4～7g g-1 h-1 , which can realize rapid dehumidification of closed environment, thereby reducing the harm caused by high humidity, and has a good application prospect in the field of space dehumidification.
(6)本发明的冰模板法可用于制备互联多孔结构聚合物凝胶，通过改变预冻温度实现对聚合物凝胶多孔结构的调控，从而实现对聚合物凝胶吸湿/脱湿动力学性能的提升，冰模板法适用于多种聚合物材料的制备，具有普适性。(6) The ice template method of the present invention can be used to prepare polymer gels with interconnected porous structures, and the regulation and control of the porous structure of the polymer gels can be realized by changing the pre-freezing temperature, thereby realizing the moisture absorption/dehydration dynamic performance of the polymer gels The ice-template method is suitable for the preparation of various polymer materials and has universal applicability.
附图说明Description of drawings
图1为本发明的光热吸湿聚合物凝胶的制备示意图。Fig. 1 is a schematic diagram of the preparation of the photothermal hygroscopic polymer gel of the present invention.
图2为实施例1中制备的光热吸湿聚合物凝胶的宏观和微观图；其中，图2(A)为冰模板法制备的光热吸湿聚合物凝胶的宏观外貌图；图2(B)为冰模板法制备的光热吸湿聚合物凝胶的微纳米尺度外貌图；图2(C)为室温聚合方法制备的光热吸湿聚合物凝胶的微纳米尺度外貌图。Fig. 2 is the macroscopic and microcosmic diagram of the photothermal moisture-absorbing polymer gel prepared in embodiment 1; Wherein, Fig. 2 (A) is the macroscopic appearance figure of the photothermal moisture-absorbing polymer gel prepared by ice template method; Fig. 2 ( B) is the micro-nano scale appearance map of the photothermal moisture-absorbing polymer gel prepared by the ice template method; Figure 2 (C) is the micro-nano scale appearance map of the photothermal moisture-absorbing polymer gel prepared by the room temperature polymerization method.
图3为实施例1中制备的光热吸湿聚合物凝胶的紫外-可见-近红外吸收光谱图。Fig. 3 is the ultraviolet-visible-near-infrared absorption spectrum diagram of the photothermal hygroscopic polymer gel prepared in Example 1.
图4为实施例1中制备的光热吸湿聚合物凝胶在不同湿度中的吸湿量统计图；其中，1为冰模板法制备的光热吸湿聚合物凝胶的吸湿量曲线；2为是室温聚合方法制备的光热吸湿聚合物凝胶的吸湿量曲线。Fig. 4 is the statistical diagram of the moisture absorption of the photothermal hygroscopic polymer gel prepared in Example 1 in different humidity; wherein, 1 is the moisture absorption curve of the photothermal hygroscopic polymer gel prepared by the ice template method; 2 is the moisture absorption curve of the photothermal hygroscopic polymer gel prepared by the ice template method; Moisture absorption curve of photothermal hygroscopic polymer gel prepared by room temperature polymerization method.
图5实施例1中制备的光热吸湿聚合物凝胶的吸湿-脱湿统计图；其中，1为冰模板法制备的光热吸湿聚合物凝胶的吸湿-脱湿曲线；2为室温聚合方法制备的光热吸湿聚合物凝胶的吸湿-脱湿曲线。The hygroscopicity-dehydration statistical diagram of the photothermal hygroscopic polymer gel prepared in Fig. 5 embodiment 1; wherein, 1 is the hygroscopicity-dehydration curve of the photothermal hygroscopic polymer gel prepared by the ice template method; 2 is the room temperature polymerization Hygroscopicity-dehydration curves of the photothermal hygroscopic polymer gel prepared by the method.
图6为实施例1中制备的光热吸湿聚合物凝胶的脱湿速度统计图；其中，1为冰模板法制备的光热吸湿聚合物凝胶的脱湿速度曲线；2为室温聚合方法制备的光热吸湿聚合物凝胶的脱湿速度曲线。Fig. 6 is a statistical diagram of the dehumidification speed of the photothermal hygroscopic polymer gel prepared in Example 1; wherein, 1 is the dehumidification speed curve of the photothermal hygroscopic polymer gel prepared by the ice template method; 2 is the room temperature polymerization method The dehydration speed curve of the prepared photothermal hygroscopic polymer gel.
图7为实施例1中制备的光热吸湿聚合物凝胶的快速吸湿-脱湿循环统计图；其中，1为冰模板法制备的光热吸湿聚合物凝胶的快速吸湿-脱湿循环曲线；2为室温聚合方法制备的光热吸湿聚合物凝胶的快速吸湿-脱湿循环曲线。Fig. 7 is the rapid moisture absorption-dehumidification cycle statistical diagram of the photothermal moisture-absorbing polymer gel prepared in Example 1; wherein, 1 is the rapid moisture absorption-dehydration cycle curve of the photothermal moisture-absorbing polymer gel prepared by the ice template method ; 2 is the rapid moisture absorption-dehydration cycle curve of the photothermal hygroscopic polymer gel prepared by the room temperature polymerization method.
图8为实施例1中制备的光热吸湿聚合物凝胶的空气取水应用实物图。FIG. 8 is a physical picture of the application of the photothermal moisture-absorbing polymer gel prepared in Example 1 for water extraction from air.
图9为实施例1中制备的光热吸湿聚合物凝胶在空气取水应用中得到的水中离子的浓度统计图。Fig. 9 is a statistical diagram of the concentration of ions in water obtained from the application of the photothermal hygroscopic polymer gel prepared in Example 1 in the application of water extraction from the air.
图10为实施例1中制备的光热吸湿聚合物凝胶应用于空间调湿的实物图。Fig. 10 is a physical picture of the photothermal moisture-absorbing polymer gel prepared in Example 1 applied to space humidity control.
图11为实施例1中制备的光热吸湿聚合物凝胶应用于空间调湿过程的湿度-时间曲线图。Fig. 11 is a humidity-time curve diagram of the application of the photothermal hygroscopic polymer gel prepared in Example 1 in the process of spatial humidity control.
具体实施方式Detailed ways
以下结合若干实施例及附图对本发明的技术方案作进一步的解释说明，但其中的实验条件和设定参数不应视为对本发明基本技术方案的局限。并且本发明的保护范围不限于下述的实施例。The technical solution of the present invention will be further explained below in conjunction with several embodiments and accompanying drawings, but the experimental conditions and set parameters therein should not be regarded as limitations on the basic technical solution of the present invention. And the protection scope of the present invention is not limited to the following examples.
本发明实施例通过调控聚合物的种类、光热转换材料的种类、预冻温度、聚合温度、吸湿盐种类及浸泡时间等来实现互联大孔结构的光热吸湿聚合物凝胶的制备。In the embodiment of the present invention, the preparation of photothermal moisture-absorbing polymer gel with interconnected macroporous structure is realized by adjusting the type of polymer, the type of photothermal conversion material, the pre-freezing temperature, the polymerization temperature, the type of hygroscopic salt, and the soaking time.
实施例1Example 1
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.19wt％过硫酸铵、0.10wt％N,N-亚甲基双丙烯酰胺溶于19.1wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将3.8wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.38wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.19wt% ammonium persulfate and 0.10wt% N,N-methylenebisacrylamide in 19.1wt% [2-(methacryloyloxy)ethyl]dimethyl-(3 - in sulfonic acid propyl) ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 3.8wt% graphene oxide to the mixed solution, stir evenly, then add 0.38wt% tetramethylethylenediamine to obtain a precursor liquid;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-20℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-5℃下进行聚合12h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -20°C for 0.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , polymerize the pre-frozen precursor solution at -5°C for 12 hours, the macroporous structure is preserved during the polymerization process, and a gel sample is obtained;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在25℃条件下浸泡12h，随后在70℃条件下烘干6h；(3) Soak the gel sample obtained in step (2) in deionized water for 12 hours at 25°C, and then dry at 70°C for 6 hours;
(4)将步骤(3)中得到的产物浸泡到9.1wt％的氯化锂溶液中，在25℃条件下浸泡1h，随后在90℃条件下烘干48h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a 9.1wt% lithium chloride solution, soak for 1 hour at 25°C, and then dry at 90°C for 48 hours to obtain a photothermal hygroscopic polymer gel .
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
图2为本施案例制备的光热吸湿聚合物凝胶的宏观与微观图。图(2A)为本实施例制备的光热吸湿聚合物凝胶的宏观外貌，可以看到凝胶整个表面呈现黑色，并且表面有冰晶融化后形成的褶皱。图(2B)为本实施例制备的光热吸湿聚合物凝胶的微纳米尺度外貌，可以看到凝胶内部呈现互联大孔结构，大孔直径为0.3～1.5mm。图(2C)为室温聚合方法制备的光热吸湿聚合物凝胶的微纳米尺度外貌，可以看到凝胶内部孔直径为20～50μm，远小于冰模板法制备得到的光热吸湿聚合物凝胶的孔的直径。Figure 2 is the macroscopic and microscopic diagrams of the photothermal hygroscopic polymer gel prepared in this example. Figure (2A) is the macroscopic appearance of the photothermal moisture-absorbing polymer gel prepared in this example. It can be seen that the entire surface of the gel is black, and there are wrinkles formed on the surface after melting ice crystals. Figure (2B) shows the micro-nano-scale appearance of the photothermal moisture-absorbing polymer gel prepared in this example. It can be seen that the interior of the gel presents an interconnected macroporous structure with a diameter of 0.3-1.5 mm. Figure (2C) shows the micro-nano-scale appearance of the photothermal moisture-absorbing polymer gel prepared by the room temperature polymerization method. It can be seen that the inner pore diameter of the gel is 20-50 μm, which is much smaller than that of the photothermal moisture-absorbing polymer gel prepared by the ice template method. The diameter of the glue hole.
图3为本实施例制备的光热吸湿聚合物凝胶的紫外-可见-近红外吸收光谱，可以看到本实施例制备的光热吸湿聚合物凝胶在全波段范围内都具有强的吸收率。Figure 3 is the UV-visible-near-infrared absorption spectrum of the photothermal moisture-absorbing polymer gel prepared in this example. It can be seen that the photothermal moisture-absorbing polymer gel prepared in this example has strong absorption in the whole band Rate.
图4为本实施例制备的光热吸湿聚合物凝胶在25℃条件不同湿度中的吸湿量统计图。其中，曲线1为冰模板法制备光热吸湿聚合物凝胶的吸湿量曲线，在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别能达到1.08，1.22，1.52，1.89，2.36，3.22，4.65g g-1；曲线2为室温聚合方法制备光热吸湿聚合物凝胶的吸湿量曲线，在相同的相对湿度下，室温聚合制备的光热吸湿聚合物凝胶的吸湿能力分别只有0.78，0.91，1.21，1.55，1.90，2.73，3.98g g-1。Fig. 4 is a statistical diagram of the moisture absorption of the photothermal hygroscopic polymer gel prepared in this example at 25°C and different humidity. Among them, curve 1 is the moisture absorption curve of the photothermal hygroscopic polymer gel prepared by the ice template method. Under the relative humidity of 30%, 40%, 50%, 60%, 70%, 80%, and 90%, the moisture absorption capacity respectively Can reach 1.08, 1.22, 1.52, 1.89, 2.36, 3.22, 4.65gg-1 ; Curve 2 is the moisture absorption curve of photothermal hygroscopic polymer gel prepared by room temperature polymerization method. The hygroscopic capacities of the thermohygroscopic polymer gels are only 0.78, 0.91, 1.21, 1.55, 1.90, 2.73, and 3.98gg-1 , respectively.
图5为本实施例制备的光热吸湿聚合物凝胶在25℃、70％的相对湿度条件下吸湿以及在25℃、30％的相对湿度、1个太阳条件下的脱湿统计图。其中，曲线1为冰模板法制备光热吸湿聚合物凝胶的吸湿-脱湿曲线，可以看到冰模板法制备的光热吸湿聚合物凝胶在25℃、70％的相对湿度条件下具有更快的吸湿速度以及更大的吸湿量，并且在25℃、30％的相对湿度、1个太阳条件下具有更快的脱湿速度；曲线2为室温聚合方法制备的光热吸湿聚合物凝胶的吸湿-脱湿曲线，其吸湿量、吸湿速度、脱湿速度均低于冰模板法制备的光热吸湿聚合物凝胶。Fig. 5 is a graph showing the moisture absorption and dehumidification of the photothermal hygroscopic polymer gel prepared in this example under the conditions of 25°C, 70% relative humidity and 25°C, 30% relative humidity, and 1 sun. Among them, curve 1 is the moisture absorption-dehydration curve of the photothermal hygroscopic polymer gel prepared by the ice template method, and it can be seen that the photothermal hygroscopic polymer gel prepared by the ice template method has Faster moisture absorption speed and greater moisture absorption capacity, and has faster dehumidification speed under the conditions of 25°C, 30% relative humidity, and 1 sun; curve 2 is the condensation of photothermal moisture-absorbing polymer prepared by room temperature polymerization method. The moisture absorption-dehydration curve of the gel, its moisture absorption capacity, moisture absorption speed, and dehydration speed are all lower than those of the photothermal hygroscopic polymer gel prepared by the ice template method.
图6为本实施例制备的光热吸湿聚合物凝胶的脱湿速度统计图。其中，曲线1为冰模板法制备光热吸湿聚合物凝胶的脱湿速度曲线；曲线2为室温聚合方法制备光热吸湿聚合物凝胶的脱湿速度曲线。本实施例冰模板法制备的光热吸湿聚合物凝胶，在1个太阳照射条件下，脱湿速度最高达到3.7g g-1h-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.58倍。Fig. 6 is a statistical chart of the dehydration speed of the photothermal hygroscopic polymer gel prepared in this embodiment. Among them, curve 1 is the dehydration speed curve of photothermal hygroscopic polymer gel prepared by ice template method; curve 2 is the dehydration speed curve of photothermal hygroscopic polymer gel prepared by room temperature polymerization method. The photothermal moisture-absorbing polymer gel prepared by the ice template method in this example has a dehumidification rate of up to 3.7gg-1 h-1 under the condition of 1 sun irradiation, which is comparable to the photothermal moisture-absorbing polymer gel prepared by room temperature polymerization. Compared with that, the dehumidification speed is increased by 1.58 times.
图7为本实施例制备的光热吸湿聚合物凝胶在25℃、70％相对湿度条件下吸湿2h，以及在25℃、30％相对湿度、1个太阳条件下脱湿1h，快速循环4次得到快速吸湿-脱湿循环统计图。其中，曲线1为冰模板法制备光热吸湿聚合物凝胶的快速吸湿-脱湿循环曲线；曲线2为室温聚合方法制备光热吸湿聚合物凝胶的快速吸湿-脱湿循环曲线。由图7可知，冰模板法制备的光热吸湿聚合物凝胶在相同时间内具有更高的吸湿量和脱湿量，日产水量可达14.5g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，日产水量提高1.65倍。Figure 7 shows that the photothermal moisture-absorbing polymer gel prepared in this example absorbs moisture for 2 hours at 25°C, 70% relative humidity, and dehumidifies for 1 hour at 25°C, 30% relative humidity, and 1 sun. Rapid cycle 4 Obtain the fast moisture absorption-dehumidification cycle statistical diagram for the first time. Among them, curve 1 is the rapid moisture absorption-dehydration cycle curve of photothermal hygroscopic polymer gel prepared by ice template method; curve 2 is the rapid moisture absorption-dehydration cycle curve of photothermal hygroscopic polymer gel prepared by room temperature polymerization method. It can be seen from Figure 7 that the photothermal hygroscopic polymer gel prepared by the ice template method has a higher moisture absorption and dehydration capacity in the same time period, and the daily water production can reach 14.5gg-1 day-1 , compared with the photothermal hygroscopic polymer gel prepared by room temperature polymerization Compared with thermal hygroscopic polymer gel, the daily water production is increased by 1.65 times.
图8为本实施例制备的光热吸湿聚合物凝胶的空气取水应用实物图。由于本实施例制备的光热吸湿聚合物凝胶具有很强的吸湿性，可在无太阳光照射期间(夜间)吸收空气中的水蒸气，液化储存在凝胶内部，然后在太阳光照射期间(白天)，通过将凝胶转移至密封容器内，同时利用其优异的光热转换能力，加热前期储存的液态水，形成水蒸气，水蒸气在装置中上升，在玻璃板处冷凝，从而得到纯化水。Fig. 8 is an actual picture of the application of the photothermal moisture-absorbing polymer gel prepared in this example for water extraction from air. Since the photothermal moisture-absorbing polymer gel prepared in this example has strong hygroscopicity, it can absorb water vapor in the air during the absence of sunlight (at night), liquefy and store it inside the gel, and then (Daytime), by transferring the gel into a sealed container, and using its excellent light-to-heat conversion ability to heat the liquid water stored in the previous stage to form water vapor, the water vapor rises in the device and condenses on the glass plate to obtain purified water.
图9为本实施例中制备的光热吸湿聚合物凝胶在空气取水应用中得到的水中离子的浓度统计图，所制水中的钠、钾、镁、钙四种离子的含量分别为0.69，0.61，0.78，1.32mgL-1，符合WHO的饮用的标准。Figure 9 is a statistical diagram of the concentration of ions in the water obtained by the photothermal moisture-absorbing polymer gel prepared in this example in the application of air water extraction, the contents of the four ions of sodium, potassium, magnesium, and calcium in the prepared water are respectively 0.69, 0.61, 0.78, 1.32mgL-1 , in line with WHO drinking standards.
图10为本实施例制备的光热吸湿聚合物凝胶应用于空间调湿的实物图。由于本实施例制备的光热吸湿聚合物凝胶具有很强的吸湿性和吸湿速率，能够实现对密闭体系的快速除湿，从而降低体系湿度，实现对湿气的有效管理。Fig. 10 is a physical picture of the application of the photothermal moisture-absorbing polymer gel prepared in this example for space humidity control. Since the photothermal hygroscopic polymer gel prepared in this example has strong hygroscopicity and moisture absorption rate, it can realize rapid dehumidification of the closed system, thereby reducing the humidity of the system and realizing effective management of moisture.
图11为本实施例制备的光热吸湿聚合物凝胶应用于空间调湿过程的湿度曲线图，可以看到在25℃环境条件下，密闭体系的湿度从95％迅速降低到21％并达到平衡，5小时内密闭体系的湿度降低74％，实现了对空间湿度的迅速调整。Figure 11 is the humidity curve of the photothermal moisture-absorbing polymer gel prepared in this example applied to the space humidity control process. It can be seen that under the ambient condition of 25°C, the humidity of the closed system rapidly decreases from 95% to 21% and reaches Balanced, the humidity of the closed system is reduced by 74% within 5 hours, realizing the rapid adjustment of the space humidity.
实施例2Example 2
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.31wt％过硫酸铵、0.25wt％N,N-亚甲基双丙烯酰胺溶于32.1wt％的甲基丙烯酸羟乙酯溶液中，搅拌均匀，得到混合溶液，再将3.4wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.34wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.31wt% ammonium persulfate and 0.25wt% N,N-methylenebisacrylamide in 32.1wt% hydroxyethyl methacrylate solution, stir well to obtain a mixed solution, and then add 3.4wt% % graphene oxide was added to the mixed solution, stirred evenly, and then 0.34wt% tetramethylethylenediamine was added to obtain a precursor solution;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-30℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-6℃下进行聚合24h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -30°C for 0.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , polymerize the pre-frozen precursor solution at -6°C for 24 hours, the macroporous structure is preserved during the polymerization process, and a gel sample is obtained;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在25℃条件下浸泡28h，随后在80℃条件下烘干8h；(3) Soak the gel sample obtained in step (2) in deionized water for 28 hours at 25°C, and then dry at 80°C for 8 hours;
(4)将步骤(3)中得到的产物浸泡到8.1wt％的氯化锂溶液中，在25℃条件下浸泡10h，随后在90℃条件下烘干46h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in 8.1wt% lithium chloride solution, soak for 10 hours at 25°C, and then dry at 90°C for 46 hours to obtain a photothermal hygroscopic polymer gel .
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
结果表明，本实施例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别达到0.93，1.07，1.39，1.72，2.24，3.07，4.34g g-1；而在相同湿度下，室温聚合方法制备的光热吸湿聚合物凝胶的吸湿能力分别只有0.68，0.83，1.14，1.47，1.79，2.58，3.63g g-1。本实施例制备的光热吸湿聚合物凝胶脱湿速度最高可达3.1g g-1h-1，日产水量可达12.5g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.3倍，日产水量提高1.47倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this example has a hygroscopic capacity of 0.93, 1.07, 1.39 at relative humidity of 30%, 40%, 50%, 60%, 70%, 80%, and 90%, respectively. , 1.72, 2.24, 3.07, 4.34gg-1 ; while at the same humidity, the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared by room temperature polymerization method is only 0.68, 0.83, 1.14, 1.47, 1.79, 2.58, 3.63gg -1 1 . The dehumidification speed of the photothermal hygroscopic polymer gel prepared in this example can reach up to 3.1gg-1 h-1 , and the daily water production can reach 12.5gg-1 day-1 . Compared with that, the dehumidification speed is increased by 1.3 times, and the daily water production is increased by 1.47 times.
本实施例制备的光热吸湿聚合物凝胶在空气取水应用中所制的水中的钠、钾、镁、钙四种离子的含量分别为0.67，0.64，0.77，1.21mg L-1，均符合WHO的饮用的标准。The photothermal moisture-absorbing polymer gel prepared in this example contains sodium, potassium, magnesium, and calcium in the water produced in the application of water extraction from the air. The contents of the four ions are 0.67, 0.64, 0.77, and 1.21 mg L-1 WHO drinking standards.
本实施例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在6小时内从95％迅速降低到30％并达到平衡，湿度降低65％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this example can quickly reduce the humidity of the closed system from 95% to 30% within 6 hours and reach equilibrium in the process of space humidity adjustment, and the humidity is reduced by 65%, realizing the rapid reduction of space humidity. Adjustment.
实施例3Example 3
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.12wt％亚硫酸氢钠和过硫酸铵、0.05wt％N,N-亚甲基双丙烯酰胺溶于7.4wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将1.4wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.15wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.12wt% sodium bisulfite and ammonium persulfate, 0.05wt% N,N-methylenebisacrylamide in 7.4wt% [2-(methacryloxy)ethyl] di In the methyl-(3-sulfonic acid propyl) ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 1.4wt% graphene oxide to the mixed solution, stir evenly, then add 0.15wt% tetramethylethyl ether Diamine, obtain precursor solution;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-10℃的冷冻装置中预冻2.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在4℃下进行低温聚合6h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -10°C for 2.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at 4°C for 6 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在25℃条件下浸泡4h，随后在70℃条件下烘干3h；(3) Soak the gel sample obtained in step (2) in deionized water for 4 hours at 25°C, and then dry at 70°C for 3 hours;
(4)将步骤(3)中得到的产物浸泡到4.58wt％的氯化锂溶液中，在25℃条件下浸泡0.5h，随后在100℃条件下烘干12h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a 4.58wt% lithium chloride solution, soak it at 25°C for 0.5h, and then dry it at 100°C for 12h to obtain a photothermal hygroscopic polymer gel glue.
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
结果表明，本实施例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别达到0.7，0.88，1.07，1.43，1.90，2.64，3.65g g-1；而在相同湿度下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有0.54，0.66，0.85，1.19，1.63，2.35，3.34g g-1。本实施例制备的光热吸湿聚合物凝胶的脱湿速度最高可达2.4g g-1h-1，日产水量可达3.36g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.4倍，日产水量提高1.53倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this example has a moisture absorption capacity of 0.7, 0.88, 1.07, respectively, at relative humidity of 30%, 40%, 50%, 60%, 70%, 80%, and 90%. , 1.43, 1.90, 2.64, 3.65gg-1 ; while at the same humidity, the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared by room temperature polymerization is only 0.54, 0.66, 0.85, 1.19, 1.63, 2.35, 3.34gg -1 . The dehumidification rate of the photothermal hygroscopic polymer gel prepared in this example can reach up to 2.4gg-1 h-1 , and the daily water production can reach 3.36gg-1 day-1 . Compared with glue, the dehumidification speed is increased by 1.4 times, and the daily water production is increased by 1.53 times.
本实施例制备的光热吸湿聚合物凝胶在空气取水应用中所制的水中钠、钾、镁、钙四种离子的含量分别为0.64，0.64，0.79，1.27mg L-1，均符合WHO的饮用的标准。The photothermal moisture-absorbing polymer gel prepared in this example has the contents of sodium, potassium, magnesium, and calcium in the water produced inthe application of water extraction from the air, respectively. drinking standards.
本实施例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在7小时内从95％迅速降低到34％并达到平衡，湿度降低61％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this example can quickly reduce the humidity of the closed system from 95% to 34% within 7 hours and reach equilibrium in the process of space humidity adjustment, and the humidity is reduced by 61%. Adjustment.
实施例4Example 4
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.49wt％过硫酸铵、0.35wt％乙二醇二甲基丙烯酸酯溶于36.8wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将6.9wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.61wt％四甲基乙二胺，得到前驱液；(1) Dissolving 0.49wt% ammonium persulfate and 0.35wt% ethylene glycol dimethacrylate in 36.8wt% [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonate In acid propyl) ammonium hydroxide solution, stir evenly, obtain mixed solution, then join 6.9wt% graphene oxide in mixed solution, stir evenly, then add 0.61wt% tetramethylethylenediamine, obtain precursor solution;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-100℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-15℃下进行低温聚合48h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -100°C for 0.5 hours to pre-freeze. During the pre-freezing process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at -15°C for 48 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在40℃条件下浸泡36h，随后在90℃条件下烘干16h；(3) Soak the gel sample obtained in step (2) in deionized water, soak at 40°C for 36h, and then dry at 90°C for 16h;
(4)将步骤(3)中得到的产物浸泡到37.5wt％的氯化锂溶液中，在40℃条件下浸泡64h，随后在130℃条件下烘干30h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a 37.5wt% lithium chloride solution, soak at 40°C for 64h, and then dry at 130°C for 30h to obtain a photothermal hygroscopic polymer gel .
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
结果表明，本实施例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别达到1.41，1.53，1.82，2.18，2.64，3.48，4.9g g-1；而在相同湿度下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有1.12，1.24，1.54，1.88，2.21，3.03，4.22g g-1。本实施例所制备的光热吸湿聚合物凝胶脱湿速度最高可达7g g-1h-1，日产水量可达20.86g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.4倍，日产水量提高1.48倍。The results show that the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared in this example reaches 1.41, 1.53, 1.82 respectively at relative humidity of 30%, 40%, 50%, 60%, 70%, 80%, and 90%. , 2.18, 2.64, 3.48, 4.9gg-1 ; while at the same humidity, the hygroscopic capacity of photothermal hygroscopic polymer gel prepared by room temperature polymerization method is only 1.12, 1.24, 1.54, 1.88, 2.21, 3.03, 4.22gg-1 respectively . The dehumidification speed of the photothermal hygroscopic polymer gel prepared in this example can reach up to 7g g-1 h-1 , and the daily water production can reach 20.86gg-1 day-1 . Compared with glue, the dehumidification speed is increased by 1.4 times, and the daily water production is increased by 1.48 times.
本实施例制备的光热吸湿聚合物凝胶在空气取水应用中所制的水中钠、钾、镁、钙四种离子的含量分别为0.67，0.67，0.78，1.27mg L-1，均符合WHO的饮用的标准。The photothermal moisture-absorbing polymer gel prepared in this example has the contents of sodium, potassium, magnesium, and calcium in the water produced inthe application of water extraction from the air, respectively. drinking standards.
本实施例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在8小时内从95％迅速降低到19％并达到平衡，湿度降低76％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this example can rapidly reduce the humidity of the closed system from 95% to 19% and reach equilibrium within 8 hours during the space humidity adjustment process, and the humidity is reduced by 76%, realizing the rapid reduction of the space humidity. Adjustment.
实施例5Example 5
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.28wt％过硫酸铵、0.17wt％N,N-亚甲基双丙烯酰胺溶于30.1wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将5.1wt％石墨加入到混合溶液中，搅拌均匀，随后加入0.51wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.28wt% ammonium persulfate and 0.17wt% N,N-methylenebisacrylamide in 30.1wt% [2-(methacryloyloxy)ethyl]dimethyl-(3 -In the ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 5.1wt% graphite to the mixed solution, stir evenly, then add 0.51wt% tetramethylethylenediamine to obtain a precursor solution;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-60℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-25℃下进行低温聚合48h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -60°C for 0.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at -25°C for 48 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在10℃条件下浸泡36h，随后在50℃条件下烘干16h；(3) Soak the gel sample obtained in step (2) in deionized water for 36 hours at 10°C, and then dry at 50°C for 16 hours;
(4)将步骤(3)中得到的产物浸泡到29.1wt％的氯化锂溶液中，在10℃条件下浸泡64h，随后在80℃条件下烘干48h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in 29.1wt% lithium chloride solution, soak at 10°C for 64h, then dry at 80°C for 48h to obtain a photothermal hygroscopic polymer gel .
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
结果表明，本实施例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别达到1.02，1.15，1.44，1.79，2.26，3.10，4.51g g-1；而在相同湿度下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有0.74，0.85，1.17，1.51，1.83，2.66，3.85g g-1。本实施例制备的光热吸湿聚合物凝胶脱湿速度最高可达3.4g g-1h-1，日产水量可达13.7g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.4倍，日产水量提高1.50倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this example has a hygroscopic capacity of 1.02, 1.15, 1.44 at relative humidity of 30%, 40%, 50%, 60%, 70%, 80%, and 90%, respectively. , 1.79, 2.26, 3.10, 4.51gg-1 ; while at the same humidity, the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared by room temperature polymerization is only 0.74, 0.85, 1.17, 1.51, 1.83, 2.66, 3.85gg -1 . The dehumidification rate of the photothermal hygroscopic polymer gel prepared in this example can reach up to 3.4gg-1 h-1 , and the daily water production can reach 13.7gg-1 day-1 . Compared with that, the dehumidification speed is increased by 1.4 times, and the daily water production is increased by 1.50 times.
本实施例制备的光热吸湿聚合物凝胶在空气取水应用中所制的水中钠、钾、镁、钙四种离子的含量分别为0.67，0.67，0.78，1.27mg/L-1，均符合WHO的饮用的标准。The photothermal moisture-absorbing polymer gel prepared in this example contains sodium, potassium, magnesium, and calcium ions in the water produced inthe application of water extraction from the air, respectively. WHO drinking standards.
本实施例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在8小时内从95％迅速降低到36％并达到平衡，湿度降低59％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this example can quickly reduce the humidity of the closed system from 95% to 36% within 8 hours and reach equilibrium in the process of space humidity adjustment, and the humidity is reduced by 59%. Adjustment.
实施例6Example 6
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.27wt％过硫酸铵、0.23wt％N,N-亚甲基双丙烯酰胺溶于26.8wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将5.3wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.53wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.27wt% ammonium persulfate and 0.23wt% N,N-methylenebisacrylamide in 26.8wt% [2-(methacryloyloxy)ethyl]dimethyl-(3 - in sulfonic acid propyl) ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 5.3wt% graphene oxide to the mixed solution, stir evenly, then add 0.53wt% tetramethylethylenediamine to obtain a precursor liquid;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-30℃的冷冻装置中预冻1.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-10℃下进行低温聚合18h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -30°C for 1.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at -10°C for 18 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在35℃条件下浸泡16h，随后在75℃条件下烘干9h；(3) Soak the gel sample obtained in step (2) in deionized water for 16 hours at 35°C, and then dry at 75°C for 9 hours;
(4)将步骤(3)中得到的产物浸泡到42.6wt％的氯化钙溶液中，在35℃条件下浸泡56h，随后在70℃条件下烘干45h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in 42.6wt% calcium chloride solution, soak at 35°C for 56h, and then dry at 70°C for 45h to obtain a photothermal hygroscopic polymer gel .
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
结果表明，本实施例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别能达到0.82，0.96，1.27，1.61，2.09，2.96，4.40gg-1；而在相同湿度下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有0.51，0.66，0.94，1.29，1.65，2.49，3.68g g-1。本实施例制备的光热吸湿聚合物凝胶脱湿度最高可达2.4g g-1h-1，日产水量可达11.5g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.3倍，日产水量提高1.32倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this example can respectively reach 0.82, 0.96, 0.96, 1.27, 1.61, 2.09, 2.96, 4.40gg-1 ; while at the same humidity, the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared by room temperature polymerization is only 0.51, 0.66, 0.94, 1.29, 1.65, 2.49, 3.68gg -1 1 . The dehumidification of the photothermal hygroscopic polymer gel prepared in this example can reach up to 2.4gg-1 h-1 , and the daily water production can reach 11.5gg-1 day-1 , which is comparable to the photothermal hygroscopic polymer gel prepared by polymerization at room temperature Compared with that, the dehumidification speed is increased by 1.3 times, and the daily water production is increased by 1.32 times.
本实施例制备的光热吸湿聚合物凝胶在空气取水过程中所制的水中钠、钾、镁、钙四种离子的含量分别为0.69，0.67，0.79，1.29mg L-1，均符合WHO的饮用的标准。The photothermal moisture-absorbing polymer gel prepared in this example contains sodium, potassium, magnesium, and calcium ions in the water produced during the process of water extraction from the air, respectively 0.69, 0.67, 0.79, and 1.29 mg L-1 , all in compliance with WHO drinking standards.
本实施例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在7小时内从95％迅速降低到37％并达到平衡，湿度降低58％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this example can quickly reduce the humidity of the closed system from 95% to 37% within 7 hours and reach equilibrium in the process of space humidity adjustment, and the humidity is reduced by 58%, realizing the rapid reduction of space humidity. Adjustment.
实施例7Example 7
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.19wt％过硫酸铵、0.10wt％N,N-亚甲基双丙烯酰胺溶于9.1wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将3.8wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.38wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.19wt% ammonium persulfate and 0.10wt% N,N-methylenebisacrylamide in 9.1wt% [2-(methacryloyloxy)ethyl]dimethyl-(3 - in sulfonic acid propyl) ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 3.8wt% graphene oxide to the mixed solution, stir evenly, then add 0.38wt% tetramethylethylenediamine to obtain a precursor liquid;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-20℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-5℃下进行低温聚合12h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -20°C for 0.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at -5°C for 12 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在25℃条件下浸泡12h，随后在70℃条件下烘干6h；(3) Soak the gel sample obtained in step (2) in deionized water for 12 hours at 25°C, and then dry at 70°C for 6 hours;
(4)将步骤(3)中得到的产物浸泡到9.1wt％的氯化锂溶液中，在25℃条件下浸泡1h，随后在90℃条件下烘干48h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a 9.1wt% lithium chloride solution, soak for 1 hour at 25°C, and then dry at 90°C for 48 hours to obtain a photothermal hygroscopic polymer gel .
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
结果表明，本实施例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别能达到0.89，1.01，1.32，1.67，2.09，2.99，4.36gg-1；而在相同湿度下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有0.71，0.83，1.14，1.46，1.78，2.69，3.84g g-1。本实施例制备的光热吸湿聚合物凝胶的脱湿度最高可达3.3g g-1h-1，日产水量可达12.8g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.46倍，日产水量提高1.58倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this example can respectively reach 0.89, 1.01, 0.89, 1.01, 1.32, 1.67, 2.09, 2.99, 4.36gg-1 ; while at the same humidity, the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared by room temperature polymerization is only 0.71, 0.83, 1.14, 1.46, 1.78, 2.69, 3.84gg- 1 . The dehumidification of the photothermal hygroscopic polymer gel prepared in this example can reach up to 3.3gg-1 h-1 , and the daily water production can reach 12.8gg-1 day-1 , compared with the photothermal hygroscopic polymer gel prepared by polymerization at room temperature Compared with that, the dehumidification speed increased by 1.46 times, and the daily water production increased by 1.58 times.
本实施例制备的光热吸湿聚合物凝胶在空气取水过程中所制的水中钠、钾、镁、钙四种离子的含量分别为0.73，0.69，0.77，1.34mg L-1,均符合WHO的饮用的标准。The photothermal moisture-absorbing polymer gel prepared in this example contains sodium, potassium, magnesium, and calcium ions inthe water produced during the process of water extraction from the air. drinking standards.
本实施例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在7小时内从95％迅速降低到27％并达到平衡，湿度降低68％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this example can rapidly reduce the humidity of the closed system from 95% to 27% within 7 hours and reach equilibrium during the space humidity control process, and the humidity is reduced by 68%, realizing the rapid improvement of the space humidity. Adjustment.
实施例8Example 8
本实施例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of the present embodiment are as follows:
(1)将0.19wt％过硫酸铵、0.10wt％N,N-亚甲基双丙烯酰胺溶于29.1wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将3.8wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.38wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.19wt% ammonium persulfate and 0.10wt% N,N-methylenebisacrylamide in 29.1wt% [2-(methacryloyloxy)ethyl]dimethyl-(3 - in sulfonic acid propyl) ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 3.8wt% graphene oxide to the mixed solution, stir evenly, then add 0.38wt% tetramethylethylenediamine to obtain a precursor liquid;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-20℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-5℃下进行低温聚合12h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -20°C for 0.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at -5°C for 12 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在25℃条件下浸泡12h，随后在70℃条件下烘干6h；(3) Soak the gel sample obtained in step (2) in deionized water for 12 hours at 25°C, and then dry at 70°C for 6 hours;
(4)将步骤(3)中得到的产物浸泡到9.1wt％的氯化锂溶液中，在25℃条件下浸泡1h，随后在90℃条件下烘干48h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a 9.1wt% lithium chloride solution, soak for 1 hour at 25°C, and then dry at 90°C for 48 hours to obtain a photothermal hygroscopic polymer gel .
对本实施例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The photothermal moisture-absorbing polymer gel prepared in this example was subjected to morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of water produced by air. , space humidity control and other properties were characterized.
结果表明，本实施例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别能达到1.16，1.34，1.69，2.06，2.59，3.53，4.90gg-1；而在相同湿度下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有0.91，1.08，1.37，1.75，2.13，2.98，4.27g g-1。本实施例制备的光热吸湿聚合物凝胶脱湿度最高可达5.5g g-1h-1，日产水量可达17.6g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.65倍，日产水量提高1.70倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this example can respectively reach 1.16, 1.34, 1.69, 2.06, 2.59, 3.53, 4.90gg-1 ; while at the same humidity, the hygroscopic capacity of photothermal hygroscopic polymer gel prepared by room temperature polymerization method is only 0.91, 1.08, 1.37, 1.75, 2.13, 2.98, 4.27gg -1 1 . The photothermal hygroscopic polymer gel prepared in this example can dehumidify up to 5.5gg-1 h-1 , and the daily water production can reach 17.6gg-1 day-1 , which is comparable to the photothermal hygroscopic polymer gel prepared by polymerization at room temperature Compared with that, the dehumidification speed is increased by 1.65 times, and the daily water production is increased by 1.70 times.
本实施例制备的光热吸湿聚合物凝胶在空气取水过程中所制的水中钠、钾、镁、钙四种离子的含量分别为0.77，0.77，0.89，1.42mg L-1,均符合WHO的饮用的标准。The photothermal moisture-absorbing polymer gel prepared in this example contains sodium, potassium, magnesium, and calcium ions in the water produced during the process of water extraction from the air. The contents of the four ions are 0.77, 0.77, 0.89, and 1.42 mg L-1 , all of which comply with the WHO drinking standards.
本实施例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在4小时内从95％迅速降低到20％并达到平衡，湿度降低75％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this example can quickly reduce the humidity of the closed system from 95% to 20% within 4 hours and reach equilibrium in the process of space humidity adjustment, and the humidity is reduced by 75%, realizing the rapid reduction of space humidity. Adjustment.
对比例1Comparative example 1
本对比例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of this comparative example are as follows:
(1)将0.19wt％过硫酸铵、0.10wt％N,N-亚甲基双丙烯酰胺溶于19.1wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将3.8wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.38wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.19wt% ammonium persulfate and 0.10wt% N,N-methylenebisacrylamide in 19.1wt% [2-(methacryloyloxy)ethyl]dimethyl-(3 - in sulfonic acid propyl) ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 3.8wt% graphene oxide to the mixed solution, stir evenly, then add 0.38wt% tetramethylethylenediamine to obtain a precursor liquid;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-20℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-5℃下进行低温聚合12h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -20°C for 0.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at -5°C for 12 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在25℃条件下浸泡12h，随后在70℃条件下烘干6h；(3) Soak the gel sample obtained in step (2) in deionized water for 12 hours at 25°C, and then dry at 70°C for 6 hours;
(4)将步骤(3)中得到的产物浸泡到3.2wt％的氯化锂溶液中，在25℃条件下浸泡1h，随后在90℃条件下烘干48h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a 3.2wt% lithium chloride solution, soak it at 25°C for 1 hour, and then dry it at 90°C for 48 hours to obtain a photothermal hygroscopic polymer gel .
对本对比例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of air-made water were carried out on the photothermal moisture-absorbing polymer gel prepared in this comparative example. , space humidity control and other properties were characterized.
结果表明，本对比例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％，70％，80％，90％的相对湿度下，吸湿能力分别能达到0.32，0.46，0.67，0.96，1.33，1.87，2.69gg-1；而在相同湿度下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有0.20，0.32，0.54，0.81，1.15，1.69，2.28g g-1。本对比例制备的光热吸湿聚合物凝胶的脱湿度最高可达0.8g g-1h-1，日产水量可达3.9g g-1day-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.3倍，日产水量提高1.30倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this comparative example can respectively reach 0.32, 0.46, 0.67, 0.96, 1.33, 1.87, 2.69gg-1 ; while at the same humidity, the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared by room temperature polymerization is only 0.20, 0.32, 0.54, 0.81, 1.15, 1.69, 2.28gg -1 1 . The dehumidification of the photothermal hygroscopic polymer gel prepared in this comparative example can reach up to 0.8gg-1 h-1 , and the daily water production can reach 3.9gg-1 day-1 . Compared with that, the dehumidification speed is increased by 1.3 times, and the daily water production is increased by 1.30 times.
本对比例制备的光热吸湿聚合物凝胶在空气取水过程中所制的水中钠、钾、镁、钙四种离子的含量分别为0.84，0.87，0.89，1.27mg L-1，均符合WHO的饮用的标准。The content of sodium, potassium, magnesium and calcium in the water produced by the photothermal moisture-absorbing polymer gel prepared in this comparative example is 0.84, 0.87, 0.89 and 1.27 mg L-1 respectively, all of which comply with WHO drinking standards.
本对比例所制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在9小时内从95％降低到57％并达到平衡，湿度降低38％，吸湿速率较慢且只能对空间湿度进行小范围的调整。The photothermal moisture-absorbing polymer gel prepared in this comparative example reduces the humidity of the closed system from 95% to 57% and reaches equilibrium in 9 hours during the space humidity adjustment process, and the humidity is reduced by 38%. Make small adjustments to the space humidity.
对比例2Comparative example 2
本对比例的光热吸湿聚合物凝胶的制备步骤如下：The preparation steps of the photothermal hygroscopic polymer gel of this comparative example are as follows:
(1)将0.19wt％过硫酸铵、0.10wt％N,N-亚甲基双丙烯酰胺溶于19.1wt％的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵溶液中，搅拌均匀，得到混合溶液，再将3.8wt％氧化石墨烯加入到混合溶液中，搅拌均匀，随后加入0.38wt％四甲基乙二胺，得到前驱液；(1) Dissolve 0.19wt% ammonium persulfate and 0.10wt% N,N-methylenebisacrylamide in 19.1wt% [2-(methacryloyloxy)ethyl]dimethyl-(3 - in sulfonic acid propyl) ammonium hydroxide solution, stir evenly to obtain a mixed solution, then add 3.8wt% graphene oxide to the mixed solution, stir evenly, then add 0.38wt% tetramethylethylenediamine to obtain a precursor liquid;
(2)将前驱液注入聚二甲基硅氧烷模具中，密封后放入-20℃的冷冻装置中预冻0.5h，预冻过程中冰晶的生长会占据体系的位置，形成大孔结构，将预冻后的前驱液在-5℃下进行低温聚合12h，在聚合的过程中大孔结构被保留下来，得到凝胶样品；(2) Inject the precursor solution into the polydimethylsiloxane mold, seal it and place it in a freezer at -20°C for 0.5 hours to pre-freeze. During the pre-freeze process, the growth of ice crystals will occupy the position of the system and form a macroporous structure , the pre-frozen precursor solution was polymerized at -5°C for 12 hours at a low temperature, and the macroporous structure was preserved during the polymerization process to obtain a gel sample;
(3)将步骤(2)中得到的凝胶样品浸泡在去离子水中，在25℃条件下浸泡12h，随后在70℃条件下烘干6h；(3) Soak the gel sample obtained in step (2) in deionized water for 12 hours at 25°C, and then dry at 70°C for 6 hours;
(4)将步骤(3)中得到的产物浸泡到44.4wt％的氯化锂溶液中，在25℃条件下浸泡1h，随后在90℃条件下烘干48h，得到光热吸湿聚合物凝胶。(4) Soak the product obtained in step (3) in a 44.4wt% lithium chloride solution, soak it at 25°C for 1 hour, and then dry it at 90°C for 48 hours to obtain a photothermal hygroscopic polymer gel .
对本对比例制备的光热吸湿聚合物凝胶进行形貌、紫外-可见-近红外吸收光谱、吸湿量、吸湿-脱湿量、吸湿速度、快速吸湿-脱湿循环、空气制水的离子浓度、空间调湿等性能进行表征。The morphology, ultraviolet-visible-near-infrared absorption spectrum, moisture absorption capacity, moisture absorption-dehumidification capacity, moisture absorption speed, rapid moisture absorption-dehumidification cycle, and ion concentration of air-made water were carried out on the photothermal moisture-absorbing polymer gel prepared in this comparative example. , space humidity control and other properties were characterized.
结果表明，本对比例制备的光热吸湿聚合物凝胶在30％，40％，50％，60％的相对湿度下，吸湿能力分别能达到2.10，2.66，3.27，3.98g g-1，但在70％～90％湿度下凝胶在吸湿过程出现漏水情况，难以将吸附的水储存在凝胶内部，并且凝胶漏水时会带走部分吸湿性无机盐，导致凝胶中盐含量降低，因此所制备的光热吸湿聚合物凝胶难以应用于70％以上的湿度；而在相同湿度(30％～60％)下，室温聚合方法制备光热吸湿聚合物凝胶的吸湿能力分别只有1.71，2.26，2.94，3.73g g-1。本对比例制备的光热吸湿聚合物凝胶的脱湿度最高可达2.8g g-1h-1，与室温聚合制备的光热吸湿聚合物凝胶相比，脱湿速度提高1.43倍，日产水量提高1.44倍。The results show that the photothermal moisture-absorbing polymer gel prepared in this comparative example can reach 2.10, 2.66, 3.27, 3.98gg-1 under the relative humidity of 30%, 40%, 50%, and 60% respectively, but in At 70% to 90% humidity, the gel will leak water during the moisture absorption process, and it is difficult to store the adsorbed water inside the gel, and when the gel leaks, it will take away part of the hygroscopic inorganic salt, resulting in a decrease in the salt content in the gel, so The prepared photothermal hygroscopic polymer gel is difficult to apply to a humidity above 70%; and at the same humidity (30%-60%), the hygroscopic capacity of the photothermal hygroscopic polymer gel prepared by room temperature polymerization is only 1.71, 2.26, 2.94, 3.73gg-1 . The photothermal moisture-absorbing polymer gel prepared in this comparative example can dehumidify up to 2.8gg-1 h-1 , compared with the photothermal moisture-absorbing polymer gel prepared by room temperature polymerization, the dehumidification speed is increased by 1.43 times, and the daily water production Increased by 1.44 times.
本对比例制备的光热吸湿聚合物凝胶在空气取水过程中所制的水中钠、钾、镁、钙四种离子的含量分别为0.79，0.72，0.84，1.23mg L-1，均符合WHO的饮用的标准。The contents of sodium, potassium, magnesium and calcium in the water produced by the photothermal hygroscopic polymer gel prepared in this comparative example are 0.79, 0.72, 0.84 and 1.23 mg L-1 respectively, all of which comply with WHO drinking standards.
本对比例制备的光热吸湿聚合物凝胶在空间调湿过程中使密闭体系湿度在4小时内从95％迅速降低到20％并达到平衡，湿度降低75％，实现了对空间湿度的迅速调整。The photothermal moisture-absorbing polymer gel prepared in this comparative example can quickly reduce the humidity of the closed system from 95% to 20% within 4 hours and reach equilibrium in the process of space humidity adjustment, and the humidity is reduced by 75%, realizing the rapid improvement of space humidity. Adjustment.
应当指出，以上所述本发明的具体实施方式，并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形，均应包含在本发明权利要求的保护范围内。It should be pointed out that the specific implementation manners of the present invention described above do not constitute a limitation to the protection scope of the present invention. Any other corresponding changes and modifications made according to the technical concept of the present invention shall be included in the protection scope of the claims of the present invention.
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