WO2022078032A1 - 一种多重响应纳米纤维素复合膜及其制备方法 - Google Patents

一种多重响应纳米纤维素复合膜及其制备方法 Download PDF

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WO2022078032A1
WO2022078032A1 PCT/CN2021/111101 CN2021111101W WO2022078032A1 WO 2022078032 A1 WO2022078032 A1 WO 2022078032A1 CN 2021111101 W CN2021111101 W CN 2021111101W WO 2022078032 A1 WO2022078032 A1 WO 2022078032A1
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nanocellulose
response
cnc
deep
composite membrane
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龙柱
孟亚会
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/04—Oxycellulose; Hydrocellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • the invention relates to a multi-response nanocellulose composite membrane and a preparation method thereof, belonging to the technical field of functional materials.
  • CNCs Nanocellulose crystals
  • acid hydrolysis mainly including sulfuric acid, hydrochloric acid and phosphoric acid.
  • 64wt% sulfuric acid hydrolysis is the most commonly used method, which can produce rod-like CNCs with a diameter of 5–10 nm and a length of 100–300 nm with negatively charged sulfuric acid half-ester groups on the surface.
  • the suspension belongs to the isotropic phase. When the suspension reaches the critical concentration of CNC, the suspension begins to exhibit the characteristics of a cholesteric liquid crystal phase.
  • the pitch of CNC suspensions is usually on the micrometer scale, and the increase in CNC concentration during evaporation causes the pitch to decrease, reaching the visible wavelength range to give the film color.
  • Many methods can adjust the pitch and thus control the color of CNC films.
  • the prepared films are often extremely fragile.
  • water-soluble polymers such as polyethylene glycol (PEG), polyvinyl alcohol (PVA), water-based polyurethane (WPU) and polyvinylpyrrolidone (PVP) have been used to reduce the brittleness of CNC films, while maintain its unique color.
  • 1-allyl-3-methylimidazolium chloride (AmimCl) was also used to increase the flexibility of the films while maintaining the iridescence of the CNC films.
  • AmimCl 1-allyl-3-methylimidazolium chloride
  • ultrasonic treatment is essential when introducing the above-mentioned polymers as plasticizers.
  • excessive sonication irreversibly inhibits the self-assembly of CNCs, resulting in the loss of film color.
  • the present invention uses nanocellulose crystal (CNC) as the base material, deep co-solvent (DES) as the plasticizer and hygroscopic agent, and anthocyanin as the pH indicator, and the solution is stirred at room temperature until the solution is mixed. uniform, and then cast in a Teflon disk and dried at room temperature to obtain a multi-response nanocellulose composite membrane.
  • Deep co-solvents can be used both as plasticizers to improve the flexibility of CNC films and as hygroscopic agents to tune the photonic bandgap of composite films.
  • the first object of the present invention is to provide a multi-responsive nanocellulose composite membrane, the components include nanocellulose crystals (CNC), deep co-solvent (DES), and anthocyanin; wherein the deep co-solvent is composed of Choline chloride and biological sugar are composed; the mass ratio of nanocellulose crystal (CNC), deep co-solvent (abbreviated as DES) and anthocyanin is 10:0-10:1, and the amount of deep co-solvent is not 0.
  • CNC nanocellulose crystals
  • DES deep co-solvent
  • anthocyanin the mass ratio of nanocellulose crystal (CNC), deep co-solvent (abbreviated as DES) and anthocyanin is 10:0-10:1, and the amount of deep co-solvent is not 0.
  • the mass ratio of choline chloride to biological sugar is 1-20:1-6, and is further optimized to be 2:1.
  • the preparation method of the deep co-solvent DES is as follows: mixing choline chloride and biological sugar in a mass ratio of 1-20:1-6, and stirring at 70-90° C. After 8-12 hours, a colorless and transparent solution, the deep co-solvent DES, was obtained.
  • the preparation method of the deep co-solvent is as follows: mixing choline chloride and glucose in a mass ratio of 2:1, heating and stirring for 10 hours in an oil bath at 80° C. to obtain Colorless and transparent solution, i.e. deep co-solvent DES.
  • the biological sugar includes one or more of glucose and sucrose.
  • the second object of the present invention is to prepare the method for the multi-response nanocellulose composite membrane of the present invention, comprising the following steps:
  • microcrystalline cellulose is obtained through acidolysis to obtain a nanocellulose suspension; then concentrate to obtain a nanocellulose concentrate;
  • the deep co-solvent is composed of choline chloride and biological sugar; the mass ratio of nanocellulose crystal (CNC), deep co-solvent (DES) and anthocyanin is 10:0-10:1, and The amount of deep co-solvent is not zero.
  • the acidolysis described in step (1) is to put microcrystalline cellulose into sulfuric acid solution for acidolysis, and the mass-volume ratio of microcrystalline cellulose to sulfuric acid solution is 10-20 g: 100mL, the concentration of sulfuric acid solution is 60-65wt%, and further optimization is: put 11g of microcrystalline cellulose into 100mL sulfuric acid solution with a concentration of 64wt% for acidolysis.
  • the concentration of the nanocellulose suspension described in step (1) is 0.5-0.8 wt %.
  • the concentrated solution described in step (1) is concentrated to a solid content of 5-8 wt %.
  • the uniform mixing in step (2) is stirring at 200-600 rpm for 10-60 min.
  • the film-forming by casting in step (3) is to cast the film-forming liquid in a polytetrafluoroethylene disc with a thickness of 50-60 ⁇ m, more preferably 52.8-54.1 ⁇ m.
  • the drying in step (3) is drying at room temperature (20-30° C.) for 10-30 hours.
  • the multiple response is a dual response of humidity and pH
  • the humidity range is a relative humidity (RH) between 30% and 95%
  • the pH range is 2-12.
  • the third object of the present invention is the application of the multiple-response nanocellulose composite membrane of the present invention in acid-base gas detection and humidity sensor.
  • the fourth object of the present invention is to provide a flexible humidity and pH dual-response sensor, which includes the multiple-response nanocellulose composite membrane described in this application.
  • the deep co-solvent used in the present invention is environmentally friendly, can be used as a plasticizer to improve the flexibility of the film, and can also be used as a hygroscopic agent to impart different colors to the nanocellulose film.
  • the anthocyanins used in the present invention are safe and nontoxic.
  • the multiple response membrane prepared by the present invention has reversibility and multiple response functions.
  • Figure 1 is a polarizing microscope image of CNC/Anth.
  • Figure 2 is a polarizing microscope image of CNC/Anth/DES 0.2 .
  • Figure 3 is a polarizing microscope image of CNC/Anth/DES 0.4 .
  • Figure 4 is a polarizing microscope image of CNC/Anth/DES 0.6 .
  • Figure 5 is a polarizing microscope image of CNC/Anth/DES 0.8 .
  • Figure 6 is a polarizing microscope image of CNC/Anth/DES 1.0 .
  • Figure 7 is a graph showing the change in fingerprint structure spacing and DES content of CNC/Anth, CNC/Anth/DES 0.2 , CNC/Anth/DES 0.4 , CNC/Anth/DES 0.6 , CNC/Anth/DES 0.8 , CNC/Anth/DES 1.0 .
  • CNC/Anth/DES 0.2 is a graph of water absorption for CNC/Anth, CNC/Anth/DES 0.2 , CNC/Anth/DES 0.4 , CNC/Anth/DES 0.6 , CNC/Anth/DES 0.8 , CNC/Anth/DES 1.0 .
  • Figure 9 is a graph of the cycle stability of CNC/Anth, CNC/Anth/DES 0.2 , CNC/Anth/DES 0.4 , CNC/Anth/DES 0.6 , CNC/Anth/DES 0.8 , CNC/Anth/DES 1.0 .
  • Tensile strength and elongation at break The composite films were tested for mechanical strength using a BZ2.5/TNIS Zwick material tester (Zwick, Germany) at 25°C and a humidity of 60% RH.
  • the sample size is 15 ⁇ 100mm, the clamping distance is 50mm, and the tensile speed is 50mm/min, and each sample is tested at least 5 times.
  • the method for multiple-response nanocellulose composite membrane includes the following steps:
  • the preparation method of the deep co-solvent is as follows: mixing choline chloride and glucose in a mass ratio of 2:1, heating and stirring in an oil bath at 80° C. for 10 hours to obtain a colorless and transparent solution, that is, the deep co-solvent;
  • Table 1 is the color parameter mechanical properties test results of the response films with different depths of co-solvent additions. From Table 1, it can be seen that the CNC/Anth film is very brittle due to the high stiffness of CNC, so it is difficult to measure by in-plane tensile test. With the increase of DES content, the tensile strength of the response film decreases and the elongation at break increases, which is due to the plasticizing effect of DES, which makes the movement of CNC intermolecular unrestricted, resulting in the elongation at break of the CNC composite film. rate increases. With the increase of the DES content, the color of the film changed from purple to light red.
  • Figures 1-6 are polarizing microscope images of CNC/Anth, CNC/Anth/DES 0.2 , CNC/Anth/DES 0.4 , CNC/Anth/DES 0.6 , CNC/Anth/DES 0.8 , CNC/Anth/DES 1.0 . It can be seen from Figure 1 to Figure 6 that the six CNC composite films all exhibit domain structure and fingerprint structure. The spacing of fingerprint structures and chiral nematic periodic structures varies with the amount of DES added. The relationship between the fingerprint structure spacing of the film and the amount of DES added is shown in Figure 7. It can be seen from Figure 7 that with the increase of DES content, the spacing size of the fingerprint structure of the composite film increases, which in turn leads to a red shift of the composite film.
  • Figure 8 is a water absorption graph with CNC/Anth, CNC/Anth/DES 0.2 , CNC/Anth/DES 0.4 , CNC/Anth/DES 0.6 , CNC/Anth/DES 0.8 , CNC/Anth/DES 1.0 . It can be seen from Figure 8 that when the relative humidity is lower than 75%, the water absorption of the CNC film is less than 10 wt%. Due to the addition of DES, the multi-response nanocellulose composite membrane has a higher water absorption capacity, which may be due to the fact that DES is a hydrophilic plasticizer, which increases the free volume of the CNC, resulting in that the CNC can absorb more water.
  • the color changes of the multi-response nanocellulose composite film under different humidity conditions are shown in Table 2. It can be seen from Table 2 that with the relative humidity increasing from 30% to 95%, the CNC/Anth/DES 0.4 composite films all show higher L* values, indicating that the composite films have higher brightness; a* value decreased from 1.34 to -8.12, while b* increased from -13.42 to 13.97. showed that the red color decreased and the yellow color increased as the relative humidity increased. Moreover, the ⁇ E* values of the composite films are all greater than 9, indicating that the color difference between the composite films under different humidity conditions is very obvious and easy to distinguish with the naked eye.
  • the CNC/Anth/DES 0.4 film with a size of 2cm ⁇ 2cm in 30%RH humidity conditions, record the color of the CNC/Anth/DES 0.4 film and measure the color parameters of the CNC/Anth/DES 0.4 film, then place it Under 95% RH humidity conditions, the color of the CNC/Anth/DES 0.4 film was recorded and the color parameters of the CNC/Anth/DES 0.4 film were measured. Repeat the above operation for more than ten times.
  • the CNC/Anth/DES 0.4 film was stored at 25°C and 30% RH, and the humidity response test was performed on the CNC/Anth/DES 0.4 film every other week, and the color and parameter values of the CNC/Anth/DES 0.4 film were recorded.
  • Example 1 The deep co-solvents in Example 1 were adjusted to be choline chloride and glycerol, and the dosage was selected to be 0.4 g, and the others were consistent with those of Example 1 to obtain a composite membrane.
  • Example 1 The deep co-solvent in Example 1 was adjusted to be choline chloride, and the dosage was selected to be 0.4 g, and the others were consistent with those of Example 1 to obtain a composite membrane.
  • Example 1 The deep co-solvent in Example 1 was adjusted to be glucose, the dosage was selected to be 0.4 g, and the others were kept the same as those of Example 1 to obtain a composite membrane.
  • Example 1 The ratio of choline chloride and glucose in Example 1 was adjusted to 1:2, the dosage was selected to be 0.4 g, and the others were the same as those in Example 1 to obtain a composite membrane.
  • Example 1 The amount of nanocellulose crystal CNC in Example 1 was adjusted to 0.5 g, and the others were the same as those in Example 1 to obtain a composite film.

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Abstract

本发明公开了一种多重响应纳米纤维素复合膜及其制备方法，属于功能材料技术领域。本发明所述的多重响应纳米纤维素复合膜的组分包括纳米纤维素晶体、深度共溶剂、花青素；其中所述的深度共溶剂是由氯化胆碱和生物糖组成，氯化胆碱与生物糖的质量比为1～20：1～6；纳米纤维素晶体、深度共溶剂、花青素的质量比为10：0～10：1，且深度共溶剂的用量不为0。本发明的复合膜制备简单、易操作，条件温和、耗时短。本发明制备的多重响应膜具有湿度和pH两种检测功能，并且具有良好的柔性、可逆性和优异的稳定性等优点，可用作柔性湿度和pH传感器。

Description

一种多重响应纳米纤维素复合膜及其制备方法 技术领域
本发明涉及一种多重响应纳米纤维素复合膜及其制备方法，属于功能材料技术领域。
背景技术
纳米纤维素晶体(CNC)具有可持续，可再生、可生物降解、高强度，高光学透明度和良好的自组装能力等特性，引起了科研工作者的广泛关注。通常，CNC是酸水解法从纤维素纤维中提取的，主要包括硫酸、盐酸和磷酸等。在这些酸中，64wt％硫酸水解是最常用的方法，可制得直径为5-10nm，长度为100-300nm，表面带负电荷的硫酸半酯基团的棒状CNC。在低浓度的CNC中，悬浮液属于各向同性相。当悬浮液到达CNC的临界浓度时，悬浮液开始表现出胆甾型液晶相的特性。悬浮液高于CNC的临界浓度时，通过交叉偏振器可观察到剪切双折射现象。随着静置时间的增加，悬浮液自发地分离为上部分(各向同性相)和下部分(各向异性相)。各向异性的棒状CNC可以在浓缩溶液中自组装成手性向列液晶相，随着溶剂的蒸发，可以生成胆甾型CNC膜。
CNC悬浮液的间距通常在微米级别，并且在蒸发过程中CNC浓度的增加会导致螺距减小，达到可见波长范围从而使薄膜呈现颜色。许多方法(如添加电解质、超声处理、离子强度、干燥温度等)都可以调节螺距，从而控制CNC薄膜的颜色。然而，由于CNC的高度脆性，所制备的薄膜通常极易破碎。为了克服这一缺陷，水溶性聚合物，如聚乙二醇(PEG)，聚乙烯醇(PVA)，水性聚氨酯(WPU)和聚乙烯吡咯烷酮(PVP)已被用于降低CNC薄膜的脆性，同时保持其独特的颜色。此外，1-烯丙基-3-甲基咪唑氯化物(AmimCl)也被用于增加薄膜的柔韧性同时保持CNC薄膜的彩虹色。通常，为了获得具有柔韧性和可调色性的彩虹色CNC膜，在引入上述聚合物作为增塑剂时，超声处理是必不可少的。然而，过度超声会不可逆转地抑制CNC的自组装，从而导致薄膜颜色消失。
因此，一种简便的方法对于制备柔性好，可调色的虹彩CNC膜是至关重要的。
发明内容
为了解决上述至少一个问题，本发明以纳米纤维素晶体(CNC)为基材，深度共溶剂(DES)为增塑剂和吸湿剂，花青素为pH指示剂，于室温下搅拌至溶液混合均匀，然后浇铸在聚四氟乙烯盘中，室温干燥得到多重响应纳米纤维素复合膜。深度共溶剂既可用作增塑剂以改善CNC薄膜的柔韧性，又可用作吸湿剂以调节复合膜的光子带隙。
本发明的第一个目的是提供一种多重响应纳米纤维素复合膜，组分包括纳米纤维素晶体 (CNC)、深度共溶剂(DES)、花青素；其中所述的深度共溶剂是由氯化胆碱和生物糖组成；纳米纤维素晶体(CNC)、深度共溶剂(简称DES)、花青素的质量比为10：0～10：1，且深度共溶剂的用量不为0。
在本发明的一种实施方式中，所述的氯化胆碱与生物糖的质量比为1～20：1～6，进一步优化为2：1。
在本发明的一种实施方式中，所述的深度共溶剂DES的制备方法为：将氯化胆碱和生物糖按质量比为1～20：1～6混合，在70～90℃下搅拌8～12h，得到无色透明溶液，即深度共溶剂DES。
在本发明的一种实施方式中，所述的深度共溶剂的制备方法为：将氯化胆碱和葡萄糖按质量比2：1混合，在80℃油浴锅中，加热并搅拌10h，得到无色透明溶液，即深度共溶剂DES。
在本发明的一种实施方式中，所述的生物糖包括葡萄糖、蔗糖中的一种或多种。
本发明的第二个目的是制备本发明所述的多重响应纳米纤维素复合膜的方法，包括如下步骤：
(1)将微晶纤维素经过酸解得到纳米纤维素悬浮液；之后浓缩，得到纳米纤维素浓缩液；
(2)在纳米纤维素浓缩液中加入深度共溶剂和花青素，混合均匀得到成膜液；
(3)将成膜液浇铸成膜，干燥，得到多重响应纳米纤维素复合膜；
其中，所述的深度共溶剂是由氯化胆碱和生物糖组成；纳米纤维素晶体(CNC)、深度共溶剂(DES)、花青素的质量比为10：0～10：1，且深度共溶剂的用量不为0。
在本发明的一种实施方式中，步骤(1)所述的酸解是将微晶纤维素放入硫酸溶液中进行酸解，微晶纤维素和硫酸溶液的质量体积比为10～20g：100mL，硫酸溶液的浓度为60-65wt％，进一步优化为：将11g微晶纤维素放入100mL浓度为64wt％的硫酸溶液中进行酸解。
在本发明的一种实施方式中，步骤(1)所述的纳米纤维素悬浮液的浓度为0.5～0.8wt％。
在本发明的一种实施方式中，步骤(1)所述的浓缩液是浓缩为固含量为5～8wt％。
在本发明的一种实施方式中，步骤(2)所述的混合均匀是200～600rpm下搅拌10～60min。
在本发明的一种实施方式中，步骤(3)所述的浇铸成膜是将成膜液浇铸在聚四氟乙烯盘中，厚度为50～60μm，进一步优选为52.8～54.1μm。
在本发明的一种实施方式中，步骤(3)所述的干燥是室温(20-30℃)下干燥10-30h。
在本发明的一种实施方式中，所述的多重响应是湿度和pH双响应，湿度范围是相对湿度(RH)介于30％和95％之间；pH范围是2-12。
本发明的第三个目的是本发明所述的多重响应纳米纤维素复合膜在酸碱性气体检测、湿度传感器中的应用。
本发明的第四个目的是提供一种柔性湿度和pH双响应传感器，其中包括本申请所述的多重响应纳米纤维素复合膜。
本发明的有益效果：
(1)本发明中纳米纤维素悬浮液制备过程简单、易操作。
(2)本发明采用的深度共溶剂，绿色环保，既能作增塑剂，提高膜的柔韧性，又能作吸湿剂，赋予纳米纤维素薄膜不同颜色。
(3)本发明采用的花青素安全无毒。
(4)本发明制备得到的多重响应膜具有可逆性和多种响应功能。
附图说明
图1是CNC/Anth的偏光显微镜图。
图2是CNC/Anth/DES 0.2的偏光显微镜图。
图3是CNC/Anth/DES 0.4的偏光显微镜图。
图4是CNC/Anth/DES 0.6的偏光显微镜图。
图5是CNC/Anth/DES 0.8的偏光显微镜图。
图6是CNC/Anth/DES 1.0的偏光显微镜图。
图7是CNC/Anth、CNC/Anth/DES 0.2、CNC/Anth/DES 0.4、CNC/Anth/DES 0.6、CNC/Anth/DES 0.8、CNC/Anth/DES 1.0的指纹结构间距与DES含量变化图。
图8是CNC/Anth、CNC/Anth/DES 0.2、CNC/Anth/DES 0.4、CNC/Anth/DES 0.6、CNC/Anth/DES 0.8、CNC/Anth/DES 1.0的吸水率图。
图9是CNC/Anth、CNC/Anth/DES 0.2、CNC/Anth/DES 0.4、CNC/Anth/DES 0.6、CNC/Anth/DES 0.8、CNC/Anth/DES 1.0的循环稳定性图。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。
测试方法：
拉伸强度和断裂伸长率：在25℃和湿度RH为60％的条件下，使用BZ2.5/TNIS Zwick材料测试仪(Zwick，德国)对复合膜进行机械强度测试。样品尺寸为15×100mm，夹距为50mm，拉伸速度为50mm/min，每个样品至少测试5次。
颜色参数的测试：使用RX100 III相机拍摄薄膜图像，并使用便携式色度计6(Xrite2600d，MI，101，USA)测量薄膜的颜色参数。
实施例1
多重响应纳米纤维素复合膜的方法，包括如下步骤：
(1)将11g微晶纤维素放入100mL浓度为64wt％的硫酸溶液中进行酸解，得到浓度为0.5wt％的纳米纤维素悬浮液；之后室温蒸发得到固含量为5wt％的纳米纤维素浓缩液(浓缩液中纳米纤维素晶体CNC的量为1g)；
(2)在纳米纤维素浓缩液中加入0.1g的花青素Anth和不同用量(0、0.2、0.4、0.6、0.8、1.0g)的深度共溶剂DES；室温搅拌均匀得到成膜液；其中深度共溶剂的制备方法为：将氯化胆碱和葡萄糖按质量比2：1混合，在80℃油浴锅中，加热并搅拌10h，得到无色透明溶液，即深度共溶剂；
(3)将成膜液浇铸在聚四氟乙烯盘中，室温干燥24h，得到多重响应纳米纤维素复合膜，分别标记为CNC/Anth、CNC/Anth/DES 0.2、CNC/Anth/DES 0.4、CNC/Anth/DES 0.6、CNC/Anth/DES 0.8、CNC/Anth/DES 1.0。
将得到的多重响应纳米纤维素复合膜进行性能测试，测试结果如下：
表1为不同深度共溶剂添加量的响应膜的颜色参数机械性能测试结果。从表1可以看出：由于CNC的高刚度，CNC/Anth膜非常脆，因此很难通过面内拉伸测试进行测量。随着DES含量的增加，响应膜的拉伸强度降低，断裂伸长率增加，这是由于DES的增塑作用，使CNC分子间的运动不受限制，从而导致了CNC复合膜的断裂伸长率增加。随这DES含量增加，薄膜颜色发生变化，由紫色逐渐变为浅红色。
表1 不同深度共溶剂添加量的响应膜的颜色参数机械性能
Figure PCTCN2021111101-appb-000001
注：“-”表示无法通过面内拉伸测试进行测量。
图1-图6是CNC/Anth、CNC/Anth/DES 0.2、CNC/Anth/DES 0.4、CNC/Anth/DES 0.6、 CNC/Anth/DES 0.8、CNC/Anth/DES 1.0的偏光显微镜图。从图1-图6可以看出：六种CNC复合膜均呈现畴结构和指纹结构。指纹结构和手性向列周期性结构的间距大小随DES添加量的不同而变化。薄膜的指纹结构间距与DES添加量的关系如图7，由图7可知，随着DES含量的增加，复合膜的指纹结构的间距尺寸增大，进而导致复合膜发生红移。
将饱和的盐溶液CaCl 2、K 2CO 3和NaCl溶液和蒸馏水置于封闭的器皿中，以控制不同的湿度条件(30％RH、50％RH、75％RH、95％RH)。将2cm×2cm的CNC/Anth、CNC/Anth/DES 0.2、CNC/Anth/DES 0.4、CNC/Anth/DES 0.6、CNC/Anth/DES 0.8、CNC/Anth/DES 1.0响应膜，放入上述器皿中，然后密封，通过对湿度响应膜进行称重，计算膜的吸水率。吸水率(％)＝(吸水后膜的重量-原始膜的重量)/原始膜的重量×100％。
图8是具有CNC/Anth、CNC/Anth/DES 0.2、CNC/Anth/DES 0.4、CNC/Anth/DES 0.6、CNC/Anth/DES 0.8、CNC/Anth/DES 1.0的吸水率图。从图8可以看出：当相对湿度低于75％时，CNC膜的吸水率小于10wt％。由于DES的加入，多重响应纳米纤维素复合膜具有更高的吸水能力，可能是由于DES是亲水性的增塑剂，增加了CNC的自由体积，导致CNC可以吸收更多的水。
以CNC/Anth/DES 0.4膜为例，在不同湿度条件下，多重响应纳米纤维素复合膜的颜色变化如表2。从表2可以看出：随着相对湿度从30％增加到95％，CNC/Anth/DES 0.4复合膜的均显示出较高的L*值，表明复合膜具有较高的亮度；a*值从1.34减小到-8.12，而b*从-13.42增大到13.97。表明，随着相对湿度增加，红色减弱和黄色增强。并且，复合膜的ΔE*值均大于9，表明不同湿度条件下复合膜之间色差非常明显，易于用肉眼分辨。
表2 CNC/Anth/DES 0.4膜在不同湿度条件下的颜色变化
Figure PCTCN2021111101-appb-000002
注：“-”代表不用比较，ΔE表示相邻湿度的颜色差值。
将2cm×2cm大小的CNC/Anth/DES 0.4膜，放入30％RH湿度条件下，记录CNC/Anth/DES 0.4膜的颜色并测量CNC/Anth/DES 0.4膜的颜色参数，然后将其放在95％RH湿度条件下，记录CNC/Anth/DES 0.4膜的颜色并测量CNC/Anth/DES 0.4膜的颜色参数。循环重复上述操作十次以上。将CNC/Anth/DES 0.4膜，放置在25℃、30％RH下存储，每隔一周，对 CNC/Anth/DES 0.4膜进行湿度响应测试，记录CNC/Anth/DES 0.4膜颜色和参数值。
CNC/Anth/DES 0.4膜的循环稳定性如图9。从图9可以看出：在相对湿度30％和95％条件下，在10个循环内，CNC/Anth/DES 0.4膜的多次循环响应的L*、a*、b*变化特别小，表明复合膜具有良好的可逆稳定性。
将2cm×2cm大小的CNC/Anth/DES 0.4膜，放入不同pH缓冲液中，记录CNC/Anth/DES 0.4膜的颜色并测量CNC/Anth/DES 0.4膜的颜色参数，如表3。
表3 CNC/Anth/DES 0.4膜在不同pH条件下的颜色变化
pH 原始 2 4 6 8 10 12
颜色 黄色 绿 浅绿 黄褐 棕色 黄绿 绿色
L * 68.73 63.56 70.43 56.98 45.51 58.41 46.15
a * -1.25 -21.12 -18.01 -3.24 10.37 -6.53 -25.10
b * 17.19 16.00 11.23 15.76 6.62 21.73 17.05
ΔE - 20.57 8.93 20.48 20.01 26.08 22.74
注：“-”代表不用比较，ΔE为相邻pH的颜色差值。
对照例1
调整实施例1中深度共溶剂为氯化胆碱和甘油，用量选择0.4g，其他和实施例1保持一致，得到复合膜。
对照例2
调整实施例1中深度共溶剂为氯化胆碱，用量选择0.4g，其他和实施例1保持一致，得到复合膜。
对照例3
调整实施例1中深度共溶剂为葡萄糖，用量选择0.4g，其他和实施例1保持一致，得到复合膜。
对照例4
调整实施例1中氯化胆碱和葡萄糖的比例为1：2，用量选择0.4g，其他和实施例1保持一致，得到复合膜。
对照例5
调整实施例1中纳米纤维素晶体CNC的用量为0.5g，其他和实施例1保持一致，得到复合膜。
将对照例1-5得到的复合膜进行性能测试，测试结果如下：
由表4可知，氯化胆碱的加入，导致复合膜的拉伸强度和断裂伸长率都减小。氯化胆碱/甘油作共溶剂时，复合膜的拉伸强度略增加，但是在复合膜存储过程中，甘油容易从复合膜中析出，导致复合膜容易老化，变脆。葡萄糖的加入，由于CNC的刚性特质，无法进行强度测试。氯化胆碱和葡萄糖的比例为1：2时，复合膜的拉伸强度略增加，断裂伸长率略较小。当CNC含量为0.5g时，复合膜厚度减小，拉伸强度降低，断裂伸长率增加。
表4 对照例1-5得到的复合膜的颜色参数机械性能
Figure PCTCN2021111101-appb-000003
注：“-”表示无法通过面内拉伸测试进行测量。
由表5可知，对照例1-4制备的膜，其在不同湿度条件下，色差均小于CNC/Anth/DES 0.4膜的色差。并且对照例2和对照例3制备得到的膜，其在较高的湿度条件下，色差小于5，无法满足智能比色的要求。对照例5制备的膜没有湿度响应作用，由于CNC含量较少，无法在自组装过程中形成光子结构，因此，无法对湿度做出响应。
表5 对照例1-5得到的复合膜的在不同湿度条件下的颜色变化ΔE
湿度(％) 对照例1 对照例2 对照例3 对照例4 对照例5
30 - - - - -
50 13.10 10.21 6.12 15.10 -
75 7.85 6.52 4.56 12.24 -
95 5.01 4.81 4.78 6.19 -
注：“-”表示没有颜色变化，ΔE代表相邻湿度之间的色差。
由表6可知，对照例1-5制备的复合膜在不同pH条件下的色差较小，无法满足智能比色的要求。
表6 对照例1-5得到的复合膜的在不同pH条件下的颜色变化ΔE
pH 对照例1 对照例2 对照例3 对照例4 对照例5
原始 - - - - -
2 14.29 15.36 2.11 16.24 5.42
4 4.35 4.79 2.43 5.12 3.51
6 3.27 4.21 1.89 4.57 2.99
8 3.01 3.97 1.62 4.61 3.12
10 4.65 4.65 4.26 4.97 2.74
12 5.24 5.66 5.31 6.25 6.23
注：“-”代表不用比较，ΔE代表相邻pH之间的色差。

Claims (13)

  1. 一种多重响应纳米纤维素复合膜，其特征在于，组分包括纳米纤维素晶体、深度共溶剂、花青素；其中所述的深度共溶剂是由氯化胆碱和生物糖组成；纳米纤维素晶体、深度共溶剂、花青素的质量比为10：0～10：1，且深度共溶剂的用量不为0。
  2. 根据权利要求1所述的多重响应纳米纤维素复合膜，其特征在于，所述的氯化胆碱与生物糖的质量比为1～20：1～6。
  3. 根据权利要求1或2所述的多重响应纳米纤维素复合膜，其特征在于，所述的生物糖包括葡萄糖、蔗糖中的一种或两种。
  4. 根据权利要求1或2所述的多重响应纳米纤维素复合膜，其特征在于，所述的深度共溶剂的制备方法为：将氯化胆碱和生物糖按质量比为1～20：1～6混合，在70～90℃下搅拌8～12h，得到无色透明溶液，即深度共溶剂。
  5. 根据权利要求2所述的多重响应纳米纤维素复合膜，其特征在于，所述的氯化胆碱与生物糖的质量比为2：1。
  6. 制备权利要求1～5任一项所述的多重响应纳米纤维素复合膜的方法，其特征在于，包括如下步骤：
    (1)将微晶纤维素经过酸解得到纳米纤维素悬浮液；之后浓缩，得到纳米纤维素浓缩液；
    (2)在纳米纤维素浓缩液中加入深度共溶剂和花青素，混合均匀得到成膜液；
    (3)将成膜液浇铸成膜，干燥，得到多重响应纳米纤维素复合膜；
    其中，所述的深度共溶剂是由氯化胆碱和生物糖组成；纳米纤维素晶体、深度共溶剂、花青素的质量比为10：0～10：1，且深度共溶剂的用量不为0。
  7. 根据权利要求6所述的方法，其特征在于，步骤(1)所述的酸解是将微晶纤维素加入硫酸溶液中进行酸解，纤维素纳米晶体CNC和硫酸溶液的质量体积比为10～20g：100mL，硫酸溶液的浓度为60-65wt％。
  8. 根据权利要求6所述的方法，其特征在于，步骤(1)所述的纳米纤维素悬浮液的浓度为0.5～0.8wt％。
  9. 根据权利要求6所述的方法，其特征在于，步骤(1)所述的浓缩液是浓缩为固含量为5～8wt％。
  10. 根据权利要求6或7所述的方法，其特征在于，步骤(3)所述的浇铸成膜是将成膜液浇铸在聚四氟乙烯盘中，厚度为50～60μm。
  11. 根据权利要求6或7所述的方法，其特征在于，所述的多重响应是湿度和pH双响应，湿度范围是相对湿度(RH)介于30％～95％之间；pH范围是2～12。
  12. 权利要求1～5任一项所述的多重响应纳米纤维素复合膜在酸碱性气体检测、湿度传感器中的应用。
  13. 一种柔性湿度和pH双响应传感器，其特征在于，其中包括权利要求1～5任一项所述的多重响应纳米纤维素复合膜。
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