WO2019144654A1 - 纳米纸、纳米纸的制备方法及柔性电子器件 - Google Patents

纳米纸、纳米纸的制备方法及柔性电子器件 Download PDF

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WO2019144654A1
WO2019144654A1 PCT/CN2018/110641 CN2018110641W WO2019144654A1 WO 2019144654 A1 WO2019144654 A1 WO 2019144654A1 CN 2018110641 W CN2018110641 W CN 2018110641W WO 2019144654 A1 WO2019144654 A1 WO 2019144654A1
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nanopaper
nanocellulose
polysaccharide
preparation
cellulose
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PCT/CN2018/110641
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English (en)
French (fr)
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李红变
刘恺然
季春燕
李新国
李文波
郭一川
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京东方科技集团股份有限公司
国家纳米科学中心
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Publication of WO2019144654A1 publication Critical patent/WO2019144654A1/zh

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose

Definitions

  • the present disclosure relates to the field of nano materials, and in particular to a nano paper, a method for preparing nano paper, and a flexible electronic device.
  • Substrate materials for flexible electronic devices typically include polymeric films such as polyimide, polyether ketone or transparent conductive polyester.
  • the polymer materials are mainly from the chemical industry, and the production process is not environmentally friendly. Moreover, most of the polymers cannot be effectively degraded and cannot be discarded at will. In addition, the heat resistance of the polymer is poor, and swelling occurs at 200 ° C, which limits the processing conditions of the device.
  • Cellulose is the most abundant natural polymer on earth. It is reported that the amount of cellulose produced by organisms is as high as 1.5 trillion tons per year. Therefore, paper made of cellulose is a flexible electronic device substrate material that is less expensive, more biocompatible, and more environmentally friendly. Since Westhouse Electronic in the 1960s discovered that paper-based vapor-free van-in-effect transistors can be used to make flexible electronic devices, paper has been used as an important substrate material for developing low-cost, foldable and disposable flexibility. Electronic devices are widely used in biosensing, radio frequency identification and other fields.
  • the present disclosure provides a nanopaper consisting of nanocellulose having a surface adsorbed with a polysaccharide having a diameter of less than 100 nm.
  • the nanocellulose has a diameter of 10 nm to 50 nm.
  • the nanocellulose contains reactive groups.
  • the reactive group is selected from the group consisting of a carboxyl group and a hydroxyl group.
  • the polysaccharide is starch, cellulose or chitin.
  • the nano paper has a thickness of 30 ⁇ m to 100 ⁇ m, and the nano paper has a roughness of less than 10 nm.
  • the present disclosure provides a method for preparing nano paper, comprising the following steps:
  • the nanocellulose is prepared by the following steps:
  • the method of oxidizing is:
  • the cellulose is added to the oxidation system for oxidation, the oxidation system comprising a catalyst and an oxidant;
  • the catalyst comprises 2,2,6,6-tetramethylpiperidine-nitrogen-oxide, and the oxidizing agent comprises sodium hypochlorite.
  • the oxidation system further comprises an auxiliary catalyst, the auxiliary catalyst being one or more of a metal bromide and a metal iodide.
  • the homogenization treatment is performed using a homogenizer at a homogenization pressure of 10,000 psi to 30,000 psi.
  • the concentration of the polysaccharide in the polysaccharide-containing solution is 0.01 wt% to 0.05 wt%.
  • the immersion temperature is 20 ° C to 50 ° C, and the immersion time is 15 hours to 30 hours.
  • the nanocellulose is dissolved in a solution containing a polysaccharide, and the concentration of the nanocellulose is 0.1 wt% to 0.5 wt%.
  • step (B) is specifically:
  • the treated nanocellulose was tiled onto a support, dried and peeled off to obtain nanopaper.
  • the present disclosure also provides a flexible electronic device comprising the above-described nanopaper; or a nanopaper prepared by the above preparation method.
  • FIG. 6 is an optical picture of a nanopaper provided by a comparative example of the present disclosure after soaking in water for 20 minutes.
  • the cellulose of the produced paper has a diameter of several tens of micrometers, and therefore the surface of the paper is usually a rough porous structure, which may cause difficulty in processing the circuit.
  • paper has hygroscopicity and is limited in its use in biological environments.
  • the nanopaper of the present disclosure provides a guarantee for the preparation of nano paper-based electronic devices and their use in biological detection.
  • nanopaper consists of nanocellulose having a surface adsorbed with a polysaccharide having a diameter of less than 100 nanometers (nm).
  • Nanocellulose refers to cellulose having a diameter of less than 100 nm.
  • the surface of the nanocellulose after oxidation treatment contains a large number of functional groups such as a hydroxyl group and a carboxyl group, and is more likely to interact with the polysaccharide to adsorb the polysaccharide.
  • the polysaccharide can interact with the nanocellulose, physically adsorbing on the surface of the nanocellulose, the interaction between the nanocellulose and the water molecule is weakened, thereby avoiding hygroscopic swelling, and therefore, the nanofiber adsorbing the polysaccharide from the surface
  • the nano paper composed of the element has good water resistance.
  • the diameter of the nanocellulose of the present disclosure may be selected from 10 nm to 50 nm, and more preferably from 20 nm to 30 nm.
  • the polysaccharide is a water-insoluble polysaccharide, and may be selected from starch, cellulose or chitin, and more preferably starch or chitin, in view of availability and dispersibility in water.
  • the thickness of the nano paper may be selected from 30 ⁇ m to 100 ⁇ m, and the roughness of the nano paper may be less than 10 nm.
  • the roughness of nanopaper is automatically calculated by atomic force scanning electron microscopy according to the peak-to-valley difference in the region, which is used to characterize the surface flatness of the material.
  • the nano-paper of the present disclosure has a light transmittance of 85% to 97%.
  • the properties of the nanopaper of the present disclosure did not change after soaking in water for 24 hours.
  • the present disclosure also provides a method for preparing nano paper, comprising the following steps:
  • the nanocellulose has a short fiber length and a reactive group such as a hydroxyl group or a carboxyl group on the surface, and the polysaccharide is easily adsorbed.
  • the diameter of the nanocellulose may be selected from 10 nm to 50 nm, and more preferably from 20 nm to 30 nm.
  • the preparation method of the nanocellulose may be subjected to enzymatic hydrolysis, acid hydrolysis or oxidation (such as nitrate oxidation, NO 2 oxidation, NaClO oxidation) treatment, and then homogenized to obtain nanocellulose.
  • enzymatic hydrolysis acid hydrolysis or oxidation (such as nitrate oxidation, NO 2 oxidation, NaClO oxidation) treatment, and then homogenized to obtain nanocellulose.
  • the preparation method of the nano cellulose is more optional:
  • the cellulose is oxidized, for example, by NaClO, and then subjected to homogenization treatment to obtain nanocellulose.
  • the oxidation of cellulose is done to reduce the hydrogen bonding interaction between the cellulose in order to save energy during the homogenization process.
  • the oxidation method can be selected as follows:
  • Oxidation is carried out by adding cellulose to an oxidation system comprising a catalyst and an oxidant; the catalyst comprising 2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO), the oxidant comprising sodium hypochlorite .
  • TEMPO 2,2,6,6-tetramethylpiperidine-nitrogen-oxide
  • the oxidation system further comprises an auxiliary catalyst, the auxiliary catalyst being one or more of a metal bromide and a metal iodide.
  • the 2,2,6,6-tetramethylpiperidine-nitrogen-oxide may be added in an amount of 0.5% to 5% by mass of the cellulose; the auxiliary catalyst may be added in an amount of 2 % ⁇ 20%; the amount of the oxidizing agent may be selected from 2% to 20% of the mass of the cellulose;
  • the homogenization treatment can be carried out using a homogenizer or an ultrasonic wave or the like.
  • the homogenization treatment is performed using a homogenizer at a homogenization pressure of 10,000 psi to 30,000 psi.
  • the surface of the nanocellulose prepared by the above method contains a large number of functional groups such as a hydroxyl group and a carboxyl group, and is more likely to interact with the polysaccharide.
  • the polysaccharide may be selected from starch, cellulose or chitin.
  • the concentration of the polysaccharide may be selected from 0.01% by weight to 0.05% by weight.
  • Polysaccharides can interact with nanocellulose and physically adsorb on the surface of nanocellulose, which weakens the interaction between nanocellulose and water molecules. Soaking is the simplest and most effective way to increase the temperature to increase the adsorption rate of polysaccharides on the surface of nanocellulose.
  • the immersion temperature is 20 ° C to 50 ° C, and the immersion time is 15 hours to 30 hours.
  • the nanocellulose After soaking, the nanocellulose is dissolved in a solution containing a polysaccharide, and the concentration of the nanocellulose may be 0.1% by weight to 0.5% by weight.
  • step (B) is specifically:
  • the treated nanocellulose was filtered and dried to obtain nanopaper. Optionally, after the treated nanocellulose is filtered, it is dried at 40 ° C to 80 ° C;
  • the treated nanocellulose was tiled onto a support, dried and peeled off to obtain nanopaper.
  • the support may for example be a petri dish having a flat surface.
  • the nano paper of the present disclosure has good stability in water, and provides a guarantee for the application of nano paper-based electronic devices in biological detection.
  • the method for treating water resistance of nano cellulose is simple, the polysaccharide used is safe and easy to obtain, the cost is low, and the nano paper is conveniently prepared on a large scale.
  • the key to limiting nano-paper-based electronic devices for bio-detection is the water resistance of nano-paper, which is currently the main reason why nano-paper electronic devices are not yet used for bio-detection.
  • the present disclosure also discloses a flexible electronic device comprising the nano paper described in the above technical solution; or a nano paper prepared by the preparation method described in the above technical solution.
  • the oxidized cellulose was homogenized by a homogenizer at a pressure of 10,000 psi to prepare a nanocellulose dispersion.
  • the nanopaper obtained in this example is shown in FIG. Characterized by atomic force scanning electron microscopy (Veeco, multimode), the results are shown in Fig. 2.
  • the nanopaper is made of 20-30 nm nanocellulose, and the surface roughness of the nanopaper is calculated to be 5.5 nm.
  • the light transmittance of the nanopaper was 96%.
  • the nanopaper obtained in this example was immersed in water for 24 hours. As shown in Fig. 4, the nanopaper could be stably existed in water, and the size and morphology did not change significantly.
  • the nanocellulose dispersion was diluted to 0.2 wt%, and starch was added to make the starch concentration 0.05 wt%, and the mixture was further stirred at 30 ° C for 20 h to lower the hydrophilicity of the nanocellulose.
  • the nanopaper was made of 10-20 nm nanocellulose, and the surface roughness of the nanopaper was calculated to be 2.0 nm. Characterized by UV-Vis/NIR absorption spectrometer (Perkin Elmer, Lambda 950), the nano-paper has a light transmission of 92%. The nanopaper obtained in this example was immersed in water for 24 hours, and the size and morphology of the nanopaper did not change significantly.
  • the nanocellulose dispersion was diluted to 0.2 wt%, and cellulose was added to make the cellulose concentration 0.01 wt%, and stirring was continued at room temperature for 20 h to lower the hydrophilicity of the nanocellulose.
  • the nanopaper was made of 30-50 nm nanocellulose, and the surface roughness of the nanopaper was calculated to be 6 nm. Characterized by UV-Vis/NIR absorption spectrometer (Perkin Elmer, Lambda 950), the nano-paper has a light transmission of 85%. The nanopaper obtained in this example was immersed in water for 24 hours, and the size and morphology of the nanopaper did not change significantly.
  • the oxidized cellulose was homogenized by a homogenizer at a pressure of 10,000 psi to prepare a nanocellulose dispersion.
  • the nanopaper obtained in this comparative example was placed in water for 20 minutes as shown in Fig. 5. As shown in Fig. 6, the nanopaper was expanded from 30 ⁇ m to 2 mm, and the mechanical properties became extremely poor, which was difficult to handle.

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Abstract

一种纳米纸、其制备方法及柔性电子器件。该纳米纸由表面吸附有多糖的纳米纤维素构成，纳米纤维素的直径小于100nm。该纳米纸的制备方法为：将纳米纤维素浸泡在含有多糖的溶液中，得到经过处理的纳米纤维素；利用该经过处理的纳米纤维素制备形成纳米纸。该纳米纸可应用在柔性电子器件中。

Description

纳米纸、纳米纸的制备方法及柔性电子器件
相关申请的交叉引用
本申请主张在2018年1月23日在中国提交的中国专利申请号No.201810063040.9的优先权，其全部内容通过引用包含于此。
技术领域
本公开涉及纳米材料领域，特别涉及一种纳米纸、纳米纸的制备方法及柔性电子器件。
背景技术
随着社会的进步和发展，人类对健康的要求越来越高。人类健康指数的实时在体监测要求开发柔性、可折叠、可穿戴或可植入的电子传感器件。
用于柔性电子器件的基底材料通常包括聚酰亚胺、聚醚酮或透明导电的聚酯等高分子薄膜。而高分子材料主要来源于化工行业，生产过程不环保，而且，大部分高分子不能有效降解，不能随意丢弃。此外，高分子的耐热性较差，在200℃时就会发生溶胀，使得器件的加工条件受到限制。
纤维素是地球上储量最丰富的天然高分子。据报道，每年由生物生产的纤维素高达1.5万亿吨。因此，由纤维素组成的纸张是一种成本更低、生物兼容性更好、且更为环保的柔性电子器件基底材料。自上世纪60年代美国西屋电子(Westhouse Electronic)发现纸上蒸镀无机场效应晶体管可以制备柔性电子器件以来，纸张已经作为一种重要的基底材料用于开发低成本、可折叠及可丢弃的柔性电子器件，并在生物传感、射频识别码等领域被广泛应用。
发明内容
本公开提供了一种纳米纸，由表面吸附有多糖的纳米纤维素构成，所述纳米纤维素的直径小于100nm。
可选地，所述纳米纤维素的直径为10nm～50nm。
可选地，所述纳米纤维素含有活性基团。
可选地，所述活性基团选自羧基和羟基。
可选地，所述多糖为淀粉、纤维素或者甲壳素。
可选地，所述纳米纸的厚度为30μm～100μm，所述纳米纸的粗糙度小于10nm。
本公开提供了一种纳米纸的制备方法，包括以下步骤：
步骤(A)：将纳米纤维素浸泡在含有多糖的溶液中，得到经过处理的纳米纤维素；
步骤(B)：利用所述经过处理的纳米纤维素制备形成纳米纸。
可选地，在所述步骤(A)之前，通过以下步骤来制备所述纳米纤维素：
步骤(C)：对纤维素进行氧化，然后经过均质处理，得到纳米纤维素。
可选地，所述氧化的方法为：
将纤维素加入氧化体系中进行氧化，所述氧化体系包括催化剂和氧化剂；
所述催化剂包括2,2,6,6-四甲基哌啶-氮-氧化物，所述氧化剂包括次氯酸钠。
可选地，所述氧化体系还包括辅助催化剂，所述辅助催化剂为金属溴化物和金属碘化物中的一种或多种。
可选地，所述均质处理为利用均质机进行处理，均质压力为10000psi～30000psi。
可选地，所述步骤(A)中，所述含有多糖的溶液中，多糖的浓度为0.01wt％～0.05wt％。
可选地，所述步骤(A)中，浸泡的温度为20℃～50℃，浸泡的时间为15小时～30小时。
可选地，所述步骤(A)中，经过浸泡，纳米纤维素溶解在含有多糖的溶液中，所述纳米纤维素的浓度为0.1wt％～0.5wt％。
可选地，所述步骤(B)具体为：
将所述经过处理的纳米纤维素过滤，压干，得到纳米纸；或者
将所述经过处理的纳米纤维素平铺至支撑物上，经过干燥，剥离，得到纳米纸。
本公开还提供了一种柔性电子器件，包括上述纳米纸；或者包括采用上 述制备方法制备的纳米纸。
附图说明
图1是本公开的一些实施例提供的纳米纸的光学图片；
图2是本公开的一些实施例提供的纳米纸的原子力扫描电镜图片；
图3是本公开的一些实施例提供的纳米纸的透过率曲线；
图4是本公开的一些实施例提供的纳米纸在水中浸泡24小时的光学图片；
图5是本公开的比较例提供的纳米纸的光学图片；以及
图6是本公开的比较例提供的纳米纸在水中浸泡20分钟后的光学图片。
具体实施方式
为了进一步理解本公开，下面结合实施例对本公开进行描述。但是应当理解，这些描述只是为进一步说明本公开的特征和优点，而不是对本公开的限制。
在相关技术中，制成纸张的纤维素直径为几十微米，因此纸张表面通常为粗糙多孔结构，造成电路可能加工困难。而且，纸张具有吸湿溶胀性，在生物环境中使用受到限制。本公开的纳米纸为纳米纸基电子器件的制备及其在生物检测中的应用提供了保障。
本公开的一些实施例提供了一种纳米纸。该纳米纸由表面吸附有多糖的纳米纤维素构成，所述纳米纤维素的直径小于100纳米(nm)。
纳米纤维素是指直径小于100nm的纤维素。经过氧化处理后的纳米纤维素表面含有大量羟基、羧基等官能团，更容易与多糖发生相互作用，从而吸附多糖。
按照本公开，由于多糖可以与纳米纤维素相互作用，在纳米纤维素表面物理吸附，使得纳米纤维素与水分子之间相互作用减弱，从而避免吸湿溶胀，因此，由表面吸附有多糖的纳米纤维素构成的纳米纸具备良好的耐水性。
本公开所述纳米纤维素的直径可选为10nm～50nm，更可选为20nm～30nm。
所述多糖为不易溶于水的多糖，考虑到易得性以及在水中的分散性，可 选为淀粉、纤维素或者甲壳素，更可选为淀粉或者甲壳素。
所述纳米纸的厚度可选为30μm～100μm，所述纳米纸的粗糙度可选小于10nm。纳米纸的粗糙度是利用原子力扫描电镜根据区域内的峰谷差值，自动计算出来的结果，用于表征材料的表面平整度。
经过试验测试，本公开的纳米纸的光透过率为85％～97％。
经过在水中浸泡24小时，本公开的纳米纸性质不发生变化。
本公开还提供了一种纳米纸的制备方法，包括以下步骤：
步骤(A)：将纳米纤维素浸泡在含有多糖的溶液中，得到经过处理的纳米纤维素；
步骤(B)：利用所述经过处理的纳米纤维素制备形成纳米纸。
按照本公开，以下具体说明制备方法：
步骤(A)：将纳米纤维素浸泡在含有多糖的溶液中，得到经过处理的纳米纤维素。
可选地，所述纳米纤维素的纤维长度短并且表面具有羟基、羧基等活性基团，容易吸附多糖。所述纳米纤维素的直径可选为10nm～50nm，更可选为20nm～30nm。
所述纳米纤维素的制备方法可以为酶解、酸解或者氧化(比如硝酸盐氧化，NO 2氧化、NaClO氧化)处理后，经过均质处理，得到纳米纤维素。
所述纳米纤维素的制备方法更可选为：
对纤维素进行氧化例如NaClO氧化，然后经过均质处理，得到纳米纤维素。
将纤维素进行氧化是为了降低纤维素之间的氢键相互作用，以便在均质过程中节约能耗。
所述氧化的方法可选为：
将纤维素加入氧化体系中进行氧化，所述氧化体系包括催化剂和氧化剂；所述催化剂包括2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)，所述氧化剂包括次氯酸钠。
可选地，所述氧化体系还包括辅助催化剂，所述辅助催化剂为金属溴化物和金属碘化物中的一种或多种。
所述2,2,6,6-四甲基哌啶-氮-氧化物的添加量可选为纤维素质量的0.5％～5％；所述辅助催化剂添加量可选为纤维素质量的2％～20％；所述氧化剂的添加量可选为纤维素质量的2％～20％；
所述均质处理可以利用均质机或者超声波等进行。
可选地，所述均质处理为利用均质机进行处理，均质压力为10000psi～30000psi。
经过上述方法制备的纳米纤维素表面含有大量羟基、羧基等官能团，更容易与多糖发生相互作用。
所述多糖可选为淀粉、纤维素或者甲壳素。所述含有多糖的溶液中，所述多糖的浓度可选为0.01wt％～0.05wt％。
多糖可以与纳米纤维素相互作用，在纳米纤维素表面物理吸附，使得纳米纤维素与水分子之间相互作用减弱。浸泡是最简单也是最有效的方式，提高温度可以提高多糖在纳米纤维素表面的吸附速度。
可选地，浸泡的温度为20℃～50℃，浸泡的时间为15小时～30小时。
经过浸泡，纳米纤维素溶解在含有多糖的溶液中，所述纳米纤维素的浓度可选为0.1wt％～0.5wt％。
步骤(B)：利用所述经过处理的纳米纤维素制备形成纳米纸。
可选地，所述步骤(B)具体为：
将所述经过处理的纳米纤维素过滤，压干，得到纳米纸。可选地，将所述经过处理的纳米纤维素过滤后，在40℃～80℃条件下压干；
或者
将所述经过处理的纳米纤维素平铺至支撑物上，经过干燥，剥离，得到纳米纸。
支撑物例如可以是表面平整的培养皿。
本公开的纳米纸在水中具有良好的稳定性，为纳米纸基电子器件在生物检测方面的应用提供了保障。同时本公开用于纳米纤维素耐水处理的方法简便、所使用的多糖安全易得，成本低，方便大规模制备纳米纸。限制纳米纸基电子器件用于生物检测的关键就是纳米纸的耐水性，这也是目前纳米纸电子器件尚没有用于生物检测的主要原因。目前增强纳米纸耐水性的方法包括 利用高价金属离子交联及化学试剂(戊二醛等)，但是这些会在纳米纸中引入金属离子，或者化学试剂毒性较大。本申请使用的多糖与纤维素成分相似，安全环保，比其他方法更具有优势。
本公开还公开了一种柔性电子器件，包括上述技术方案所述的纳米纸；或者包括采用上述技术方案所述制备方法制备的纳米纸。
为了进一步理解本公开，下面结合实施例对本公开提供的纳米纸及其制备方法进行详细说明，本公开的保护范围不受以下实施例的限制。
实施例1
(1)参照文献Zhu et al,Nanoscale,2013,5,3787对纤维素进行化学氧化。将5g漂白纸浆分散于250mL Na 2CO 3/NaHCO 3缓冲溶液(pH＝10)中，加入2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)78.1mg和NaBr 514.4mg，缓慢加入12wt％NaClO溶液3.1mL并机械搅拌4h，反应过程中用pH计测量pH值并用1M NaOH调控pH值保持10。
(2)利用均质机在10000psi压力下将氧化后的纤维素进行均质，制备纳米纤维素分散液。
(3)将纳米纤维素分散液稀释至0.2wt％，并加入甲壳素，使甲壳素浓度为0.05wt％，继续于50℃搅拌20h。
(4)将15mL甲壳素处理过的纳米纤维素分散液过滤，在60℃压干得到30μm厚度的纳米纸。
本实施例得到的纳米纸如图1所示。经原子力扫描电镜(Veeco,multimode)表征，结果如图2所示，该纳米纸由20-30nm的纳米纤维素制成，经计算，该纳米纸表面粗糙度为5.5nm。经紫外-可见/近红外吸收光谱仪(Perkin Elmer,Lambda 950)表征，结果如图3所示，该纳米纸的光透过率为96％。将本实施例得到的纳米纸在水中浸泡24h，如图4所示，纳米纸在水中可以稳定存在，尺寸和形貌均无明显变化。
实施例2
(1)参照文献Zhu et al,Nanoscale,2013,5,3787对纤维素进行化学氧化。将5g漂白牛皮纸浆分散于250mL Na 2CO 3/NaHCO 3缓冲溶液(pH＝10)中，加入2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)78.1mg和NaBr 514.4mg，缓 慢加入12wt％NaClO溶液1.5mL并机械搅拌4h，反应过程中用pH计测量pH值并用1M NaOH调控pH值保持10。
(2)利用均质机在30000psi压力下将氧化后的纤维素进行均质，制备纳米纤维素分散液。
(3)将纳米纤维素分散液稀释至0.2wt％，并加入淀粉，使淀粉浓度为0.05wt％，继续于30℃搅拌20h，降低纳米纤维素亲水性。
(4)将30mL淀粉处理过的纳米纤维素分散液浇筑在表面平整的培养皿内，于室温干燥，得到50μm厚度的纳米纸。
经原子力扫描电镜(Veeco,multimode)表征，该纳米纸由10-20nm的纳米纤维素制成，经计算，该纳米纸表面粗糙度为2.0nm。经紫外-可见/近红外吸收光谱仪(Perkin Elmer,Lambda 950)表征，该纳米纸的光透过率为92％。将本实施例得到的纳米纸在水中浸泡24h，纳米纸尺寸和形貌均无明显变化。
实施例3
(1)参照文献Zhu et al,Nanoscale,2013,5,3787对纤维素进行化学氧化。将5g漂白牛皮纸浆分散于250mL Na 2CO 3/NaHCO 3缓冲溶液(pH＝10)中，加入2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)39mg和NaBr 260mg，缓慢加入12wt％NaClO溶液3.1mL并机械搅拌4h，反应过程中用pH计测量pH值并用1M NaOH调控pH值保持10。
(2)利用均质机在30000psi压力下将氧化后的纤维素进行均质，制备纳米纤维素分散液。
(3)将纳米纤维素分散液稀释至0.2wt％，并加入纤维素，使纤维素浓度为0.01wt％，继续室温搅拌20h，降低纳米纤维素亲水性。
(4)将60mL淀粉处理过的纳米纤维素分散液过滤，于80℃压干，得到100μm厚度的纳米纸。
经原子力扫描电镜(Veeco,multimode)表征，该纳米纸由30-50nm的纳米纤维素制成，经计算，该纳米纸表面粗糙度为6nm。经紫外-可见/近红外吸收光谱仪(Perkin Elmer,Lambda 950)表征，该纳米纸的光透过率为85％。将本实施例得到的纳米纸在水中浸泡24h，纳米纸尺寸和形貌均无明显变化。
比较例1
(1)参照文献Zhu et al,Nanoscale,2013,5,3787对纤维素进行化学氧化。取将5g漂白牛皮纸浆分散于250mL Na 2CO 3/NaHCO 3缓冲溶液(pH＝10)中，加入2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)78.1mg和NaBr 514.4mg，缓慢加入12wt％NaClO溶液3.1mL并机械搅拌4h，反应过程中用pH计测量pH值并用1M NaOH调控pH值保持10。
(2)利用均质机在10000psi压力下将氧化后的纤维素进行均质，制备纳米纤维素分散液。
(3)将15mL纳米纤维素分散液过滤，在60℃压干得到30μm厚度的纳米纸。
本比较例得到的纳米纸如图5所示，将该纳米纸置于水中20分钟，如图6所示，纳米纸由30μm膨胀为2mm，而且力学性能变得极差，难以操作。
以上实施例的说明只是用于帮助理解本公开的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本公开。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本公开的精神或范围的情况下，在其它实施例中实现。因此，本公开将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (16)

  1. 一种纳米纸，由表面吸附有多糖的纳米纤维素构成，所述纳米纤维素的直径小于100nm。
  2. 根据权利要求1所述的纳米纸，所述纳米纤维素的直径为10nm～50nm。
  3. 根据权利要求1所述的纳米纸，所述纳米纤维素含有活性基团。
  4. 根据权利要求3所述的纳米纸，所述活性基团选自羧基和羟基。
  5. 根据权利要求1所述的纳米纸，所述多糖为淀粉、纤维素或者甲壳素。
  6. 根据权利要求1所述的纳米纸，所述纳米纸的厚度为30μm～100μm，所述纳米纸的粗糙度小于10nm。
  7. 一种纳米纸的制备方法，包括以下步骤：
    步骤(A)：将纳米纤维素浸泡在含有多糖的溶液中，得到经过处理的纳米纤维素；
    步骤(B)：利用所述经过处理的纳米纤维素制备形成纳米纸。
  8. 根据权利要求7所述的制备方法，在所述步骤(A)之前，包括以下步骤：
    步骤(C)：对纤维素进行氧化，然后经过均质处理，得到纳米纤维素。
  9. 根据权利要求8所述的制备方法，所述氧化的方法为：
    将纤维素加入氧化体系中进行氧化，所述氧化体系包括催化剂和氧化剂；
    所述催化剂包括2,2,6,6-四甲基哌啶-氮-氧化物，所述氧化剂包括次氯酸钠。
  10. 根据权利要求9所述的制备方法，所述氧化体系还包括辅助催化剂，所述辅助催化剂为金属溴化物和金属碘化物中的一种或多种。
  11. 根据权利要求8所述的制备方法，所述均质处理为利用均质机进行处理，均质压力为10000psi～30000psi。
  12. 根据权利要求7所述的制备方法，所述步骤(A)中，所述含有多糖的溶液中，多糖的浓度为0.01wt％～0.05wt％。
  13. 根据权利要求7所述的制备方法，所述步骤(A)中，浸泡的温度为 20℃～50℃，浸泡的时间为15小时～30小时。
  14. 根据权利要求7所述的制备方法，所述步骤(A)中，经过浸泡，纳米纤维素溶解在含有多糖的溶液中，所述纳米纤维素的浓度为0.1wt％～0.5wt％。
  15. 根据权利要求7所述的制备方法，所述步骤(B)具体为：
    将所述经过处理的纳米纤维素过滤，压干，得到纳米纸；或者
    将所述经过处理的纳米纤维素平铺至支撑物上，经过干燥，剥离，得到纳米纸。
  16. 一种柔性电子器件，包括如权利要求1～6任意一项所述的纳米纸。
PCT/CN2018/110641 2018-01-23 2018-10-17 纳米纸、纳米纸的制备方法及柔性电子器件 WO2019144654A1 (zh)

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