CN113637234B - Elastic cellulose aerogel and preparation method and application thereof - Google Patents

Elastic cellulose aerogel and preparation method and application thereof Download PDF

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CN113637234B
CN113637234B CN202110994538.9A CN202110994538A CN113637234B CN 113637234 B CN113637234 B CN 113637234B CN 202110994538 A CN202110994538 A CN 202110994538A CN 113637234 B CN113637234 B CN 113637234B
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CN113637234A (en
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秦恒飞
姜锋
周月
杨洲
柏寄荣
李溪
康诗飞
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Jiangsu University of Technology
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Abstract

The invention relates to an elastic cellulose aerogel and a preparation method and application thereof, and the preparation method comprises the following steps: (1) Freezing the nano cellulose suspension liquid by liquid nitrogen, and then carrying out freeze drying to obtain the submicron cellulose fiber; (2) Dispersing the submicron cellulose fiber in water, freezing for the second time, and then freezing and drying to obtain the elastic cellulose aerogel; the elastic cellulose aerogel is subjected to surface modification by adopting a silane compound through a chemical vapor deposition method to obtain the super-hydrophobic elastic cellulose aerogel, and the super-hydrophobic elastic cellulose aerogel is applied to the field of oil-water separation. The elastic cellulose aerogel obtained by the method has good rebound resilience and shape recovery performance under normal temperature and cold environment, and also has low heat conduction coefficient, the super-hydrophobic elastic cellulose aerogel obtained by surface modification shows super-strong separation performance in oil-water separation, and the adsorption capacity to chloroform can reach about 489 times of the self-mass.

Description

一种弹性纤维素气凝胶及其制备方法和应用A kind of elastic cellulose airgel and its preparation method and application

技术领域technical field

本发明涉及高分子材料技术领域,具体涉及一种弹性纤维素气凝胶及其制备方法和应用。The invention relates to the technical field of polymer materials, in particular to an elastic cellulose airgel and its preparation method and application.

背景技术Background technique

作为最轻的固体材料,气凝胶在热调节、能量收集和储存、传感器、环境修复、和生物医学等领域得到了广泛的应用。气凝胶的这种多样化应用归因于其众多优点,包括低密度、高孔隙率、高比表面积、低导热性和生物相容性。在气凝胶的各种物理性能中,力学性能是限制气凝胶应用的重要因素。人们在提高气凝胶的机械性能方面做了大量的努力,主要集中在提高有机气凝胶和无机气凝胶的抗压性和弹性上,其中具有高回弹性和形状快速恢复性能的气凝胶也得到了进一步的研究,因为从大压缩应变中形状快速恢复的能力对其在电信号传感、水处理、隔热和隔音、空气过滤和储能方面的应用极其重要。As the lightest solid material, aerogels have been widely used in thermal regulation, energy harvesting and storage, sensors, environmental remediation, and biomedicine. Such diverse applications of aerogels are attributed to their numerous advantages, including low density, high porosity, high specific surface area, low thermal conductivity, and biocompatibility. Among the various physical properties of aerogels, mechanical properties are an important factor limiting the application of aerogels. A lot of efforts have been made to improve the mechanical properties of aerogels, mainly focusing on improving the compression resistance and elasticity of organic aerogels and inorganic aerogels, among which aerogels with high resilience and rapid shape recovery properties Glues have also been further investigated because the ability to recover shape quickly from large compressive strains is extremely important for their applications in electrical signal sensing, water treatment, heat and sound insulation, air filtration, and energy storage.

生物衍生的天然聚合物,特别是纤维素,由于其来源广和易加工性,以此作为制备气凝胶的原料,引起了研究者的极大兴趣。传统的纤维素气凝胶合成需要大量溶剂的溶解再生过程。最近,纳米纤维素,特别是纤维素纳米纤维,已被广泛用于构建高比表面积和优异力学性能的气凝胶。由于高比表面积和丰富的极性官能团,通过冷冻干燥纳米纤维悬浮液可以方便地制备超轻纤维素气凝胶,显示出优异的结构完整性。虽然纳米纤维素气凝胶具有良好的压缩性,可压缩90%以上的应变而不断裂,但压缩后的气凝胶一般回弹性较差,无法从压缩状态恢复。缺乏回弹性的原因是由于非弹性微观结构和压缩过程中相邻纤维素纤维之间形成的强氢键。采用单次冷冻法制备的纳米纤维素气凝胶,由于其在轴向上表现出各向异性弹性,导致回弹性性能不理想。Biologically derived natural polymers, especially cellulose, have attracted great interest as raw materials for the preparation of aerogels due to their wide sources and easy processability. Conventional cellulose airgel synthesis requires a large amount of solvent for the dissolution regeneration process. Recently, nanocellulose, especially cellulose nanofibers, has been widely used to construct aerogels with high specific surface area and excellent mechanical properties. Due to the high specific surface area and abundant polar functional groups, ultralight cellulose aerogels can be conveniently prepared by freeze-drying nanofibrous suspensions, showing excellent structural integrity. Although nanocellulose airgel has good compressibility and can compress more than 90% of the strain without breaking, the compressed airgel generally has poor resilience and cannot recover from the compressed state. The reason for the lack of resilience is due to the inelastic microstructure and strong hydrogen bonds formed between adjacent cellulose fibers during compression. Nanocellulose aerogels prepared by a single freezing method have unsatisfactory resilience properties due to their anisotropic elasticity in the axial direction.

发明内容Contents of the invention

针对常规气凝胶回弹性差、无法从压缩状态恢复的技术问题,而提供一种弹性纤维素气凝胶及其制备方法和应用。本发明制得的弹性纤维素气凝胶具有较低的密度和导热系数,在常温及寒冷环境下均具有较好的弹性和形状恢复性。Aiming at the technical problem of conventional airgel having poor resilience and being unable to recover from a compressed state, an elastic cellulose airgel and its preparation method and application are provided. The elastic cellulose airgel prepared by the invention has lower density and thermal conductivity, and better elasticity and shape recovery under normal temperature and cold environment.

为了达到以上目的,本发明通过以下技术方案实现:In order to achieve the above object, the present invention is realized through the following technical solutions:

一种弹性纤维素气凝胶的制备方法,包括如下步骤:A preparation method of elastic cellulose airgel, comprising the steps of:

(1)将纳米纤维素悬浮液进行液氮冷冻,然后进行冷冻干燥得到亚微米纤维素纤维;(1) The nanocellulose suspension is frozen with liquid nitrogen, and then freeze-dried to obtain submicron cellulose fibers;

(2)将所述亚微米纤维素纤维分散于水中进行二次冷冻,然后进行冷冻干燥即制得弹性纤维素气凝胶。(2) Dispersing the submicron cellulose fibers in water for secondary freezing, and then freeze-drying to obtain the elastic cellulose airgel.

进一步地,步骤(1)中所述纳米纤维素悬浮液是将0.2wt%的纳米纤维素分散液进行离心去除沉淀后收集上层悬浮液,所述离心的转速为3000-800rpm、离心时间为5-10min,将所述上层悬浮液进行稀释得到浓度为0.05wt%的纳米纤维素悬浮液。Further, the nanocellulose suspension described in step (1) is to centrifuge 0.2wt% of the nanocellulose dispersion to remove the precipitate and collect the upper suspension, the centrifugation speed is 3000-800rpm, and the centrifugation time is 5 -10 min, dilute the upper suspension to obtain a nanocellulose suspension with a concentration of 0.05 wt%.

再进一步地,所述纳米纤维素分散液的获得采用TEMPO/NaClO氧化体系对天然纸浆进行氧化处理20min~5h,在所述氧化处理过程中,采用NaOH溶液控制氧化体系pH为9.8-10.5,氧化处理结束后,采用透析袋透析一周后,经细胞粉碎机处理25min得到纳米纤维素,稀释后,得到0.2wt%的纳米纤维素分散液;所述TEMPO、所述NaClO、所述纸浆的质量比为1:(1.4-5):1。Still further, the TEMPO/NaClO oxidation system is used to oxidize the natural pulp for 20 minutes to 5 hours to obtain the nanocellulose dispersion liquid. During the oxidation treatment process, NaOH solution is used to control the pH of the oxidation system to be 9.8-10.5. After the treatment, use a dialysis bag for dialysis for one week, and then process it with a cell pulverizer for 25 minutes to obtain nanocellulose, and after dilution, obtain a 0.2wt% nanocellulose dispersion; the mass ratio of the TEMPO, the NaClO, and the pulp is 1:(1.4-5):1.

进一步地,步骤(2)中所述亚微米纤维素纤维分散于水中后的浓度控制为0.2wt%~2wt%;优选浓度控制为0.2wt%~0.6wt%。Further, the concentration of the submicron cellulose fibers dispersed in water in step (2) is controlled to be 0.2wt%-2wt%; preferably, the concentration is controlled to be 0.2wt%-0.6wt%.

进一步地,步骤(1)中所述液氮冷冻的温度为-196℃、时间为1-2h;步骤(2)中所述二次冷冻的温度采用温度为-20℃的冰箱冷冻3h;步骤(1)和步骤(2)中所述冷冻干燥采用-55~-45℃的冷冻干燥机进行冷冻48h,冷冻压力为0.02-1Pa。Further, the temperature of liquid nitrogen freezing described in step (1) is -196°C, and the time is 1-2h; the temperature of secondary freezing described in step (2) is frozen for 3h in a refrigerator with a temperature of -20°C; step The freeze-drying described in (1) and step (2) is carried out by a freeze dryer at -55 to -45° C. for 48 hours, and the freezing pressure is 0.02-1 Pa.

本发明另一方面提供上述制备方法制得的弹性纤维素气凝胶。Another aspect of the present invention provides the elastic cellulose airgel prepared by the above preparation method.

本发明第三方面提供上述制备方法制得的弹性纤维素气凝胶在吸水性材料上的应用或者在隔热材料上的应用。The third aspect of the present invention provides the application of the elastic cellulose airgel prepared by the above preparation method on water-absorbing materials or on heat-insulating materials.

本发明第四方面提供上述制备方法制得的弹性纤维素气凝胶的应用,通过化学气相沉积法采用硅烷类化合物对所述弹性纤维素气凝胶进行表面修饰得到超疏水弹性纤维素气凝胶,将所述超疏水弹性纤维素气凝胶应用于油水分离领域。The fourth aspect of the present invention provides the application of the elastic cellulose airgel prepared by the above preparation method, and the elastic cellulose airgel is modified by chemical vapor deposition using silane compounds to obtain superhydrophobic elastic cellulose airgel glue, applying the superhydrophobic elastic cellulose airgel to the field of oil-water separation.

进一步地,所述化学气相沉积法是将所述弹性纤维素气凝胶置于不锈钢网格上方,所述不锈钢网格下方并排放置分别装有水和所述硅烷类化合物的两个容器,于密闭真空状态下在70~90℃下反应5-7h,制得超疏水弹性纤维素气凝胶。Further, in the chemical vapor deposition method, the elastic cellulose airgel is placed above the stainless steel grid, and two containers respectively containing water and the silane compound are placed side by side under the stainless steel grid, and then React at 70-90° C. for 5-7 hours in a closed vacuum state to prepare superhydrophobic elastic cellulose airgel.

再进一步地,所述弹性纤维素气凝胶、所述硅烷类化合物、所述水的用量为(20-25)mg:(1-2)mL:0.5mL;所述硅烷类化合物为甲基三甲氧基硅烷或聚二甲基硅氧烷。Still further, the amount of the elastic cellulose airgel, the silane compound, and the water is (20-25) mg: (1-2) mL: 0.5 mL; the silane compound is methyl Trimethoxysilane or Dimethicone.

有益技术效果:Beneficial technical effects:

本发明通过液氮冷冻和低温冰箱冷冻的双重冷冻法组装了弹性纤维素气凝胶,再经表面修饰得到了超疏水弹性纤维素气凝胶。本发明的弹性纤维素气凝胶的密度为2-20mg/cm3,在常温和极冷环境(-196℃)下均具有较好的形状恢复性,回弹性较佳,具有超弹性;且导热系数低,仅为0.023W/m·K,具有良好的隔热和红外屏蔽性能;此外,经过表面修饰后得到的超疏水弹性纤维素气凝胶在油水分离中表现出了超强的分离性能,对氯仿的吸附量可达约自身质量的489倍。本发明材料可用于高吸水性材料、隔热材料、油水分离等领域。The invention assembles the elastic cellulose airgel through the double freezing method of liquid nitrogen freezing and low-temperature refrigerator freezing, and then obtains the superhydrophobic elastic cellulose airgel through surface modification. The elastic cellulose aerogel of the present invention has a density of 2-20 mg/cm 3 , and has good shape recovery, good resilience and superelasticity in both normal and extremely cold environments (-196°C); and Low thermal conductivity, only 0.023W/m K, has good heat insulation and infrared shielding properties; in addition, the superhydrophobic elastic cellulose airgel obtained after surface modification shows super strong separation in oil-water separation Performance, the adsorption capacity of chloroform can reach about 489 times its own mass. The material of the invention can be used in the fields of high water absorption material, heat insulation material, oil-water separation and the like.

附图说明Description of drawings

图1为实施例1制得的的SEM形貌图,其中a表示纳米纤维素悬浮液,b表示亚微米纤维素纤维,c、d表示弹性纤维素气凝胶;abd图中标尺均为500nm,c图中标尺为500μm。Fig. 1 is the SEM topography figure that embodiment 1 makes, and wherein a represents nano-cellulose suspension, b represents submicron cellulose fiber, c, d represent elastic cellulose aerogel; Scale bar among abd figure is 500nm , The scale bar in c is 500 μm.

图2为实施例1制得的弹性纤维素气凝胶弹性应力-应变曲线图。Fig. 2 is the elastic stress-strain curve diagram of the elastic cellulose airgel prepared in Example 1.

图3为应用例1的超疏水弹性纤维素气凝胶的FTIR曲线,其中a表示实施例2的弹性纤维素气凝胶,b表示应用例1的超疏水弹性纤维素气凝胶。Figure 3 is the FTIR curve of the superhydrophobic elastic cellulose airgel of Application Example 1, wherein a represents the elastic cellulose airgel of Example 2, and b represents the superhydrophobic elastic cellulose airgel of Application Example 1.

图4为应用例1的超疏水弹性纤维素气凝胶的水接触角随时间变化图。Fig. 4 is a time-dependent graph of the water contact angle of the superhydrophobic elastic cellulose airgel of Application Example 1.

具体实施方式Detailed ways

下面将结合本发明的实施例,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,而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的,决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例,本领域普通技术人员在没有作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。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. The following description of at least one exemplary embodiment is merely illustrative in nature and in no way taken as limiting the invention, its application or uses. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

除非另外具体说明,否则在这些实施例中阐述的数值不限制本发明的范围。对于相关领域普通技术人员已知的技术、方法可能不作详细讨论,但在适当情况下,所述技术、方法应当被视为说明书的一部分。在这里示出和讨论的所有示例中,任何具体值应被解释为仅仅是示例性的,而不是作为限制。因此,示例性实施例的其它示例可以具有不同的值。The numerical values set forth in these examples do not limit the scope of the invention unless specifically stated otherwise. Techniques and methods known to those of ordinary skill in the related art may not be discussed in detail, but under appropriate circumstances, the techniques and methods should be regarded as a part of the specification. In all examples shown and discussed herein, any specific values should be construed as exemplary only, and not as limitations. Therefore, other examples of the exemplary embodiment may have different values.

实施例1Example 1

一种弹性纤维素气凝胶的制备方法,包括如下步骤:A preparation method of elastic cellulose airgel, comprising the steps of:

(1)将0.05wt%纳米纤维素悬浮液放入-196℃的液氮中进行液氮冷冻1h,接着置于温度为-55℃、压力为0.02Pa的冷冻干燥机中进行冷冻干燥48h,得到亚微米纤维素纤维;(1) Put the 0.05wt% nanocellulose suspension into liquid nitrogen at -196°C for liquid nitrogen freezing for 1 hour, then place it in a freeze dryer with a temperature of -55°C and a pressure of 0.02Pa for 48 hours, Obtain submicron cellulose fibers;

(2)将所述亚微米纤维素纤维经旋涡混合器分散于水中配制成浓度为0.2wt%的分散液,搅拌均匀后置于-20℃的冰箱中进行二次冷冻3h,接着置于温度为-55℃、压力为0.02Pa的冷冻干燥机中进行冷冻干燥48h,即制得弹性纤维素气凝胶。(2) Disperse the submicron cellulose fibers in water with a vortex mixer to prepare a dispersion with a concentration of 0.2 wt%. After stirring evenly, place it in a refrigerator at -20°C for secondary freezing for 3 hours, and then place it at temperature Freeze-drying in a freeze dryer at -55°C and a pressure of 0.02Pa for 48 hours to obtain elastic cellulose airgel.

其中步骤(1)中纳米纤维素悬浮液的获得方法:①采用TEMPO/NaClO氧化体系对天然纸浆进行氧化处理2h,在氧化处理过程中,采用NaOH溶液控制氧化体系pH为10,氧化处理结束后,采用透析袋透析一周后,经细胞粉碎机处理25min后得到纳米纤维素,稀释后,得到0.2wt%的纳米纤维素分散液;所述TEMPO、所述NaClO、所述纸浆的质量比为1:1.6:1;②将0.2wt%的纳米纤维素分散液置于离心管中,通过高速离心机进行离心,离心机转速为5000r/min,离心时间为10分钟,离心结束后去除离心管底部的白色沉淀,收集上层悬浮液,将上层悬浮液进行稀释得到浓度为0.05wt%的纳米纤维素悬浮液。Wherein the obtaining method of nano-cellulose suspension in step (1): 1. adopt TEMPO/NaClO oxidation system to carry out oxidation treatment 2h to natural paper pulp, in oxidation treatment process, adopt NaOH solution to control oxidation system pH to be 10, after oxidation treatment finishes , after one week of dialysis using a dialysis bag, nanocellulose was obtained after being treated with a cell pulverizer for 25 minutes, and after dilution, a 0.2wt% nanocellulose dispersion was obtained; the mass ratio of the TEMPO, the NaClO, and the pulp was 1 :1.6:1; ②Put 0.2wt% nanocellulose dispersion in a centrifuge tube, centrifuge through a high-speed centrifuge, the centrifuge speed is 5000r/min, and the centrifugation time is 10 minutes. After the centrifugation, remove the bottom of the centrifuge tube The white precipitate, the upper suspension was collected, and the upper suspension was diluted to obtain a nanocellulose suspension with a concentration of 0.05 wt%.

对本实施例经过步骤(1)制得的亚微米纤维素纤维已经最后制得的弹性纤维素气凝胶进行电镜的观察,如图1所示,其中a表示纳米纤维素悬浮液,b表示亚微米纤维素纤维,c、d表示弹性纤维素气凝胶;abd图中标尺为500nm,c图中标尺为500μm。由图1可知,图1a中原始态的纳米纤维素悬浮液中的纤维素宽度为3-5nm、长度至少为500nm;图1b经过液氮冷冻后得到了连续亚微米纤维素纤维,纤维宽度约100-200nm;图1c和图1d是液氮冷冻后再经过冰箱低温二次冷冻后得到的气凝胶,可见经过液氮冷冻和低温冰箱二次冷冻后,气凝胶的微观形貌呈现出蜂窝状结构。The elastic cellulose airgel that has been finally prepared by the submicron cellulose fiber prepared in step (1) in this embodiment is observed by electron microscope, as shown in Figure 1, wherein a represents the nanocellulose suspension, and b represents the submicron cellulose aerogel. Micron cellulose fibers, c and d represent elastic cellulose airgel; the scale bar in abd is 500nm, and the scale in c is 500μm. As can be seen from Figure 1, the width of cellulose in the original nanocellulose suspension in Figure 1a is 3-5nm, and the length is at least 500nm; Figure 1b obtained continuous submicron cellulose fibers after liquid nitrogen freezing, and the fiber width is about 100-200nm; Figure 1c and Figure 1d are the aerogels obtained after liquid nitrogen freezing and secondary freezing in the refrigerator. It can be seen that after liquid nitrogen freezing and low-temperature refrigerator secondary freezing, the microscopic morphology of the airgel shows Honeycomb structure.

对本实施例制得的弹性纤维素气凝胶进行应力-应变测试,测试是将制得的圆柱形气凝胶(直径21mm,高度23mm)置于Instron 3345型材料测试系统上,使用2KN测压元件将气凝胶压缩至应变达到60%。结果如图2所示,由图2可知,本实施例的气凝胶循环压应力-应变曲线在50次循环后表现出良好的弹性行为,压缩后气凝胶几乎可以恢复到原始尺寸,循环50次后不可恢复应变仅为3.8%,回弹性较好。极限应力保持0.542kPa,接近第一个循环,表明气凝胶结构保持较好。The elastic cellulose airgel prepared in this example is subjected to a stress-strain test. The test is to place the prepared cylindrical airgel (21mm in diameter, 23mm in height) on an Instron 3345 material testing system, and use 2KN pressure measurement The element compresses the airgel to a strain of 60 percent. The results are shown in Figure 2. It can be seen from Figure 2 that the cyclic compressive stress-strain curve of the airgel in this example shows good elastic behavior after 50 cycles, and the airgel can almost return to its original size after compression. After 50 times, the unrecoverable strain is only 3.8%, and the resilience is good. The ultimate stress remains at 0.542kPa, which is close to the first cycle, indicating that the airgel structure is well maintained.

本发明制得的弹性气凝胶具有较好的回弹性,这种较好的回弹性可以归因于亚微米纤维的存在。液氮冷冻过程中可以使纳米级纤维素纤维(直径3-5nm)组装成直径为100-200nm的亚微米纤维素纤维,将亚微米纤维素纤维分散在水中形成分散液后于冰箱冷冻(-20℃)过程中,由于在低冷冻速率下生长成较大的冰晶,形成了具有几百微米大孔隙的蜂窝状结构(如图1c所示),从纳米纤维(直径3-5nm)转变成亚微米纤维(直径100-200nm)过程中,由于表面积显著减小,且亚微米纤维素组装成气凝胶过程中不再形成膜的结构,抑制了相邻纤维素之间的氢键作用,而相互连接的亚微米纤维网络形成的蜂窝状结构提供了优异的弹性行为,并表现出极佳的柔韧性和可折叠性。The elastic airgel prepared by the present invention has better resilience, which can be attributed to the existence of submicron fibers. During the liquid nitrogen freezing process, nano-scale cellulose fibers (3-5nm in diameter) can be assembled into submicron cellulose fibers with a diameter of 100-200nm, and the submicron cellulose fibers are dispersed in water to form a dispersion and then frozen in the refrigerator (- 20°C), due to the growth of larger ice crystals at a low freezing rate, a honeycomb structure with large pores of several hundred micrometers (as shown in Figure 1c) is formed, transforming from nanofibers (3-5 nm in diameter) to In the process of submicron fibers (diameter 100-200nm), due to the significant reduction in surface area, and the submicron cellulose assembly into the airgel process no longer forms a film structure, inhibiting the hydrogen bonding between adjacent cellulose, The honeycomb structure formed by the interconnected submicrometer fiber network provides excellent elastic behavior and exhibits excellent flexibility and foldability.

实施例2Example 2

一种弹性纤维素气凝胶的制备方法,包括如下步骤:A preparation method of elastic cellulose airgel, comprising the steps of:

(1)将0.05wt%纳米纤维素悬浮液放入-196℃的液氮中进行液氮冷冻2h,接着置于温度为-55℃、压力为0.2Pa的冷冻干燥机中进行冷冻干燥48h,得到亚微米纤维素纤维;(1) Put 0.05wt% nanocellulose suspension into liquid nitrogen at -196°C for 2 hours, then place it in a freeze dryer with a temperature of -55°C and a pressure of 0.2Pa for 48 hours, Obtain submicron cellulose fibers;

(2)将所述亚微米纤维素纤维经旋涡混合器分散于水中配制成浓度为0.2wt%的分散液,搅拌均匀后置于-20℃的冰箱中进行二次冷冻3h,接着置于温度为-55℃、压力为0.2Pa的冷冻干燥机中进行冷冻干燥48h,即制得弹性纤维素气凝胶。(2) Disperse the submicron cellulose fibers in water with a vortex mixer to prepare a dispersion with a concentration of 0.2 wt%. After stirring evenly, place it in a refrigerator at -20°C for secondary freezing for 3 hours, and then place it at temperature Freeze-drying in a freeze dryer at -55°C and a pressure of 0.2 Pa for 48 hours to obtain elastic cellulose airgel.

实施例3Example 3

本实施例的弹性纤维素气凝胶的制备方法与实施例2相同,不同之处在于,步骤(2)中将所述亚微米纤维素纤维分散于水中配制成浓度为0.4wt%的分散液。The preparation method of the elastic cellulose airgel of this embodiment is the same as that of Example 2, except that in step (2), the submicron cellulose fibers are dispersed in water to prepare a dispersion with a concentration of 0.4 wt%. .

实施例4Example 4

本实施例的弹性纤维素气凝胶的制备方法与实施例2相同,不同之处在于,步骤(2)中将所述亚微米纤维素纤维分散于水中配制成浓度为0.6wt%的分散液。The preparation method of the elastic cellulose airgel of this embodiment is the same as that of Example 2, except that in step (2), the submicron cellulose fibers are dispersed in water to prepare a dispersion with a concentration of 0.6 wt%. .

实施例5Example 5

本实施例的弹性纤维素气凝胶的制备方法与实施例2相同,不同之处在于,步骤(2)中将所述亚微米纤维素纤维分散于水中配制成浓度为0.8wt%的分散液。The preparation method of the elastic cellulose airgel of this embodiment is the same as that of Example 2, except that in step (2), the submicron cellulose fibers are dispersed in water to prepare a dispersion with a concentration of 0.8 wt%. .

实施例2-5制得的气凝胶均具有蜂窝状微观结构形貌。The aerogels prepared in Examples 2-5 all have honeycomb microstructure morphology.

对比例1Comparative example 1

传统纤维素凝胶的制备:Preparation of traditional cellulose gel:

(1)采用TEMPO/NaClO对天然纸浆进行氧化处理2h,在所述氧化处理过程中,采用NaOH溶液控制氧化体系pH为10,采用透析袋透析一周后,经细胞粉碎机处理25min后得到纳米纤维素,稀释后,得到0.4wt%的纳米纤维素分散液;所述TEMPO、所述NaClO、所述纸浆的质量比为1:1.6:1。(1) Use TEMPO/NaClO to oxidize the natural pulp for 2 hours. In the oxidation treatment process, use NaOH solution to control the pH of the oxidation system to be 10. After dialysis with a dialysis bag for one week, nanofibers are obtained after being treated with a cell pulverizer for 25 minutes. Element, after dilution, obtain the nanocellulose dispersion liquid of 0.4wt%; The mass ratio of described TEMPO, described NaClO, described pulp is 1:1.6:1.

(2)将步骤(1)中0.4wt%的纳米纤维素分散液放置-20℃的冰箱冷冻3h,得到0.4wt%冰冻纳米纤维素;(2) Place the 0.4wt% nanocellulose dispersion in step (1) in a refrigerator at -20°C for 3 hours to obtain 0.4wt% frozen nanocellulose;

(3)将步骤(2)中的0.4wt%冰冻纳米纤维素在-55℃的冷冻干燥机中冷冻48h,冷冻压力为0.2Pa。(3) The 0.4wt% frozen nanocellulose in step (2) was frozen in a freeze dryer at -55° C. for 48 hours, and the freezing pressure was 0.2 Pa.

对比例2Comparative example 2

本对比例的纤维素气凝胶的制备方法为:将0.5wt%纳米纤维素悬浮液放入-196℃的液氮中进行液氮冷冻5min,接着置于温度为-91℃、压力为0.6Pa的冷冻干燥机中进行冷冻干燥72h,得到纤维素气凝胶。The preparation method of the cellulose airgel of this comparative example is: put 0.5wt% nanocellulose suspension into liquid nitrogen at -196°C for liquid nitrogen freezing for 5 minutes, and then place it at a temperature of -91°C and a pressure of 0.6 Carry out freeze-drying 72h in the freeze-drying machine of Pa, obtain cellulose aerogel.

对实施例1-4及对比例1-2所制得的气凝胶进行孔隙率、密度、导热系数以及回弹性的测试,测试结果见表1。其中常温回弹率的测试方法为:采用200g的砝码将直径21mm×高度23mm尺寸的气凝胶压缩至原尺寸高度的80%,计算去除200g砝码后气凝胶回弹的高度占原始尺寸高度的百分比即为初始压缩后回弹率,在此基础上进行50个压缩回弹的循环,计算50个循环后去除200g砝码后气凝胶回弹的高度占原始尺寸高度的百分比即为50个循环后的压缩回弹率。-196℃压缩回弹率的测试方法是将气凝胶置于液氮中,用力压缩气凝胶至原始尺寸的80%后,去除力,观察回弹性。The airgel prepared in Examples 1-4 and Comparative Examples 1-2 were tested for porosity, density, thermal conductivity and resilience, and the test results are shown in Table 1. The test method for the rebound rate at room temperature is: use a weight of 200g to compress the airgel with a diameter of 21mm x height of 23mm to 80% of the original height, and calculate the rebound height of the airgel after removing the weight of 200g. The percentage of the height of the size is the rebound rate after the initial compression. On this basis, 50 cycles of compression and rebound are performed, and the percentage of the height of the airgel rebound after removing the 200g weight after 50 cycles is calculated as the percentage of the original size height is It is the compression rebound rate after 50 cycles. The test method of compression resilience at -196°C is to place the airgel in liquid nitrogen, compress the airgel to 80% of its original size, remove the force, and observe the resilience.

表1实施例1-4及对比例1-2所制得的气凝胶性能The airgel performance that table 1 embodiment 1-4 and comparative example 1-2 make

Figure BDA0003233536500000061
Figure BDA0003233536500000061

由表1可知,本发明方法制得的气凝胶具有发达的孔隙结构以及非常小的密度,在常温和极冷环境(-196℃)下均具有较好的形状恢复性,回弹性较佳,具有超弹性;且导热系数低,仅为0.023-0.028W/m·K,具有良好的隔热和红外屏蔽性能。可用于高吸水性材料、隔热材料领域。It can be seen from Table 1 that the airgel prepared by the method of the present invention has a well-developed pore structure and a very small density, and has good shape recovery and better resilience in normal and extremely cold environments (-196°C). , with superelasticity; and low thermal conductivity, only 0.023-0.028W/m·K, with good heat insulation and infrared shielding properties. It can be used in the fields of super absorbent materials and heat insulation materials.

应用例1Application example 1

采用实施例2制得的弹性纤维素气凝胶通过化学气相沉积法采用甲基三甲氧基硅烷(简写MTMS)对所述弹性纤维素气凝胶进行表面修饰,得到超疏水弹性纤维素气凝胶;其中所述化学气相沉积法是将22mg所述弹性纤维素气凝胶置于不锈钢网格上方,所述不锈钢网格下方并排放置分别装有0.5mL水和1mL甲基三甲氧基硅烷的两个容器(不锈钢网格的大小需覆盖两个容器的表面积),于密闭真空状态下在80℃下反应6h后制得超疏水弹性纤维素气凝胶。The elastic cellulose airgel prepared in Example 2 is used to modify the surface of the elastic cellulose airgel by using methyltrimethoxysilane (abbreviated as MTMS) by chemical vapor deposition to obtain superhydrophobic elastic cellulose airgel Glue; wherein the chemical vapor deposition method is to place 22mg of the elastic cellulose airgel above the stainless steel grid, and place side by side below the stainless steel grid are respectively equipped with 0.5mL water and 1mL methyltrimethoxysilane Two containers (the size of the stainless steel mesh needs to cover the surface area of the two containers) were reacted at 80° C. for 6 hours in a closed vacuum state to prepare superhydrophobic elastic cellulose airgel.

对制得的超疏水弹性纤维素气凝胶进行FTIR测试,测试结果分别如图3所示。由于纤维素气凝胶是亲水性的,在温和的搅拌下可以很容易地重新分散到水中。因此为了提高弹性纤维素气凝胶的稳定性和疏水性,可以通过在80℃真空下将MTMS气相沉积6h获得超疏水弹性纤维素气凝胶。FTIR光谱证实了硅烷的成功改性。3328cm-1、1598cm-1和1032cm-1处的特征峰均为O-H伸缩振动、C=O/C=C伸缩振动和C-O伸缩振动,均出现在弹性纤维素气凝胶(实施例2产物)和超疏水弹性纤维素气凝胶(本应用例产物)中。除了具有未改性纤维素气凝胶的典型光谱特征外,MTMS改性弹性纤维素气凝胶得到的超疏水弹性纤维素气凝胶在Si-CH3和Si-O-Si的1262cm-1、776cm-1、798cm-1处均出现特征峰。The FTIR test was carried out on the prepared superhydrophobic elastic cellulose airgel, and the test results are shown in Fig. 3 respectively. Since cellulose aerogels are hydrophilic, they can be easily redispersed in water with gentle agitation. Therefore, in order to improve the stability and hydrophobicity of elastic cellulose aerogels, superhydrophobic elastic cellulose aerogels can be obtained by vapor deposition of MTMS under vacuum at 80 °C for 6 h. FTIR spectroscopy confirmed the successful modification of the silane. The characteristic peaks at 3328cm -1 , 1598cm -1 and 1032cm -1 are all OH stretching vibrations, C=O/C=C stretching vibrations and CO stretching vibrations, all appearing in elastic cellulose airgel (the product of Example 2) and superhydrophobic elastic cellulose airgel (the product of this application example). In addition to having the typical spectral features of unmodified cellulose aerogels, the superhydrophobic elastic cellulose aerogels obtained by MTMS modified elastic cellulose aerogels have a peak of 1262 cm -1 in Si- CH3 and Si-O-Si , 776cm -1 , 798cm -1 all appear characteristic peaks.

对制得的超疏水弹性纤维素气凝胶进行水接触角测试,接触角随时间变化见图4,由图4可知,测得本应用例得到的超疏水弹性纤维素气凝胶在第一次与水接触时,水接触角为164°,在7s后水接触角逐渐减小到157°,并趋于稳定,具有较好的超疏水性及一定的自清洁能力。The obtained superhydrophobic elastic cellulose airgel was tested for water contact angle, and the contact angle changes with time are shown in Fig. When contacting with water for the first time, the water contact angle is 164°, and after 7s, the water contact angle gradually decreases to 157°, and tends to be stable. It has good superhydrophobicity and certain self-cleaning ability.

将本应用例制得的超疏水弹性纤维素气凝胶应用于油水分离,有选择性的从水中将油性溶剂去除,油水分离性能的数据见表2。油水分离性能测试方法:将超疏水弹性纤维素气凝胶浸于混有油性溶剂的水中对油性溶剂进行吸附,以超疏水弹性纤维素气凝胶吸附油性溶剂后的重量与干燥气凝胶重量比值表示增重(wt%)来评价油水分离性能。The superhydrophobic elastic cellulose airgel prepared in this application example is applied to oil-water separation, and the oily solvent is selectively removed from water. The data of oil-water separation performance are shown in Table 2. Oil-water separation performance test method: soak the superhydrophobic elastic cellulose airgel in water mixed with oily solvent to absorb the oily solvent, the weight of the superhydrophobic elastic cellulose airgel after absorbing the oily solvent and the weight of the dry airgel The ratio represents the weight gain (wt%) to evaluate the oil-water separation performance.

表2油水分离性能Table 2 Oil-water separation performance

Figure BDA0003233536500000071
Figure BDA0003233536500000071

Figure BDA0003233536500000081
Figure BDA0003233536500000081

由表2可知,采用本发明的弹性纤维素气凝胶对其进行低表面能改性得到的超疏水弹性纤维素气凝胶对大多数油类溶剂表现出较高的吸附能力,对氯仿、泵油、菜籽油吸附后的增重分别达到了48886%、25765%、23416%。本发明的超疏水弹性纤维素气凝胶可以以其自身重量的159-489倍吸收大多数油类溶剂,具有较好的油水分离效果。As can be seen from Table 2, the superhydrophobic elastic cellulose airgel obtained by modifying the elastic cellulose aerogel of the present invention with low surface energy shows a higher adsorption capacity to most oil solvents, and has a higher adsorption capacity to chloroform, The weight gains of pump oil and rapeseed oil after adsorption reached 48886%, 25765%, and 23416%, respectively. The superhydrophobic elastic cellulose airgel of the present invention can absorb most oil solvents at 159-489 times its own weight, and has better oil-water separation effect.

以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.

Claims (8)

1.一种弹性纤维素气凝胶的制备方法,其特征在于,包括如下步骤:1. a preparation method of elastic cellulose airgel, is characterized in that, comprises the steps: (1) 将纳米纤维素悬浮液进行液氮冷冻,然后进行冷冻干燥得到亚微米纤维素纤维;(1) The nanocellulose suspension is frozen in liquid nitrogen, and then freeze-dried to obtain submicron cellulose fibers; 所述纳米纤维素悬浮液是将0.2wt%的纳米纤维素分散液进行离心去除沉淀后收集上层悬浮液,将所述上层悬浮液进行稀释得到浓度为0.05wt%的纳米纤维素悬浮液;The nanocellulose suspension is obtained by centrifuging 0.2wt% of the nanocellulose dispersion to remove the precipitate and collecting the upper suspension, and diluting the upper suspension to obtain a nanocellulose suspension with a concentration of 0.05wt%; 所述纳米纤维素分散液的获得采用TEMPO/NaClO氧化体系对天然纸浆进行氧化处理20min~5h,在所述氧化处理过程中,采用NaOH溶液控制氧化体系pH为9.8-10.5,氧化处理结束后,采用透析袋透析一周后,经细胞粉碎机处理得到纳米纤维素,稀释后,得到0.2wt%的纳米纤维素分散液;所述TEMPO、所述NaClO、所述纸浆的质量比为1:(1.4-5):1;The nanocellulose dispersion is obtained by using a TEMPO/NaClO oxidation system to oxidize the natural pulp for 20 minutes to 5 hours. During the oxidation treatment, NaOH solution is used to control the pH of the oxidation system to be 9.8-10.5. After the oxidation treatment is completed, After adopting dialysis bags for dialysis for one week, the cell pulverizer is processed to obtain nanocellulose, and after dilution, a 0.2wt% nanocellulose dispersion is obtained; the mass ratio of the TEMPO, the NaClO, and the pulp is 1:(1.4 -5):1; 所述液氮冷冻的温度为-196℃、时间为1-2h;The freezing temperature of the liquid nitrogen is -196°C and the time is 1-2h; (2)将所述亚微米纤维素纤维分散于水中进行二次冷冻,然后进行冷冻干燥即制得弹性纤维素气凝胶;所述亚微米纤维素纤维分散于水中后的浓度控制为0.2wt%~2wt%;所述二次冷冻的温度采用温度为-20℃的冰箱冷冻3h。(2) Disperse the submicron cellulose fibers in water for secondary freezing, and then freeze-dry to obtain elastic cellulose airgel; the concentration of the submicron cellulose fibers dispersed in water is controlled to 0.2wt %~2wt%; the temperature of the secondary freezing adopts a refrigerator with a temperature of -20° C. for 3 hours. 2.根据权利要求1所述的一种弹性纤维素气凝胶的制备方法,其特征在于,所述离心的转速为5000rpm、离心时间为10min;所述细胞粉碎机处理的时间为25min。2. The preparation method of a kind of elastic cellulose airgel according to claim 1, characterized in that, the centrifugation speed is 5000rpm, and the centrifugation time is 10min; the treatment time of the cell pulverizer is 25min. 3.根据权利要求1所述的一种弹性纤维素气凝胶的制备方法,其特征在于,步骤(1)和步骤(2)中所述冷冻干燥采用-55~-45℃的冷冻干燥机进行冷冻48h,冷冻压力为0.02-1Pa。3. the preparation method of a kind of elastic cellulose airgel according to claim 1 is characterized in that, the freeze-drying described in step (1) and step (2) adopts the freeze-drying machine of-55~-45 ℃ Freeze for 48 hours, and the freezing pressure is 0.02-1Pa. 4.根据权利要求1-3任一项所述的制备方法制得的弹性纤维素气凝胶。4. The elastic cellulose airgel prepared by the preparation method according to any one of claims 1-3. 5.根据权利要求1-3任一项所述的制备方法制得的弹性纤维素气凝胶在吸水性材料或者在隔热材料上的应用。5. The application of the elastic cellulose airgel prepared by the preparation method according to any one of claims 1-3 on a water-absorbing material or on a heat-insulating material. 6.一种弹性纤维素气凝胶的应用,其特征在于,所述弹性纤维素气凝胶根据权利要求1-3任一项所述的制备方法制得,通过化学气相沉积法采用硅烷类化合物对所述弹性纤维素气凝胶进行表面修饰,得到超疏水弹性纤维素气凝胶,将所述超疏水弹性纤维素气凝胶应用于油水分离领域。6. An application of elastic cellulose airgel, characterized in that, said elastic cellulose airgel is prepared according to the preparation method described in any one of claims 1-3, by chemical vapor deposition using silanes The compound modifies the surface of the elastic cellulose airgel to obtain a superhydrophobic elastic cellulose airgel, and the superhydrophobic elastic cellulose airgel is applied to the field of oil-water separation. 7.根据权利要求6所述的应用,其特征在于,所述化学气相沉积法是将所述弹性纤维素气凝胶置于不锈钢网格上方,所述不锈钢网格下方并排放置分别装有水和所述硅烷类化合物的两个容器,于密闭真空状态下在70~90℃下反应5-7h,制得超疏水弹性纤维素气凝胶。7. The application according to claim 6, characterized in that, the chemical vapor deposition method is to place the elastic cellulose aerogel above the stainless steel grid, and place side by side below the stainless steel grid to be filled with water respectively. react with two containers of the silane compound in a sealed vacuum state at 70-90° C. for 5-7 hours to prepare superhydrophobic elastic cellulose airgel. 8.根据权利要求6所述的应用,其特征在于,所述弹性纤维素气凝胶、所述硅烷类化合物、所述水的用量为(20-25)mg:(1-2)mL:0.5mL;所述硅烷类化合物为甲基三甲氧基硅烷或聚二甲基硅氧烷。8. application according to claim 6, is characterized in that, the consumption of described elastic cellulose airgel, described silane compound, described water is (20-25) mg: (1-2) mL: 0.5 mL; the silane compound is methyltrimethoxysilane or polydimethylsiloxane.
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