WO2022088339A1 - 一种波长可控纤维素虹彩膜及其制备方法 - Google Patents

一种波长可控纤维素虹彩膜及其制备方法 Download PDF

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WO2022088339A1
WO2022088339A1 PCT/CN2020/131752 CN2020131752W WO2022088339A1 WO 2022088339 A1 WO2022088339 A1 WO 2022088339A1 CN 2020131752 W CN2020131752 W CN 2020131752W WO 2022088339 A1 WO2022088339 A1 WO 2022088339A1
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cellulose
cnc
solution
lactic acid
wavelength
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French (fr)
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王斌
曾劲松
陈克复
段承良
程峥
李金鹏
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华南理工大学
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
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    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
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    • C08L1/10—Esters of organic acids, i.e. acylates
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    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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    • C08K5/00—Use of organic ingredients
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    • C08K5/15—Heterocyclic compounds having oxygen in the ring
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    • C08L2203/16—Applications used for films

Definitions

  • the invention belongs to the field of preparation of functional film materials, in particular to a wavelength-controllable cellulose iris film and a preparation method thereof.
  • cellulose As the main component of plant cell walls, cellulose is the most widely distributed and most abundant renewable polysaccharide in nature. It has excellent biocompatibility and biodegradability, so it is widely used in the preparation and research of functional materials.
  • CNC Cellulose nanocrystals
  • CNC In the preparation of CNC by sulfuric acid hydrolysis, the hydroxyl groups on the cellulose surface were converted into sulfate esters, which introduced a negative surface charge, thereby forming a stable aqueous dispersion of CNC.
  • CNC self-assembles to form a stable lyotropic chiral nematic structure under certain concentration conditions, which is widely used in anti-counterfeiting materials, sensors and optical devices due to its excellent optical properties.
  • the iris film prepared by pure CNC has the disadvantages of high brittleness, and the wavelength is greatly affected by external conditions and is not easy to control, which seriously affects the practicability of CNC iris film.
  • a pure mechanical energy input method is adopted to obtain the desired or predetermined iridescent wavelength.
  • the wavelength can be controlled to a certain extent, the method of pure mechanical energy input has high energy consumption and high cost, and is not suitable for large-scale production of enterprises.
  • the purpose of the present invention is to provide a wavelength-controllable cellulose iris film and a preparation method thereof.
  • the invention realizes the controllability of different color wavelengths and simultaneously improves the brittleness of the pure CNC film.
  • a preparation method of a wavelength range controllable cellulose iris film comprising the following steps:
  • the CNC suspension is a cellulose nanocrystal suspension
  • the volume ratio of CNC suspension to lactic acid solution and glucose solution described in step (1) is (12-8): 1: (2-3);
  • the concentration of cellulose nanocrystals in the CNC suspension described in step (1) is 3-4wt%;
  • the concentration of the lactic acid solution is 8-10wt%; the concentration of the glucose solution is 10-20wt%;
  • the solvent of lactic acid solution is water; the solvent of glucose solution is water.
  • volume ratio of the CNC solution to the lactic acid solution and the glucose solution is 12:1:3, it shows blue after film formation, and when the volume ratio is 11:1:2, it shows green after film formation, and the volume ratio is 10:1 : 2, yellow after film formation, 9:1:2, orange after film formation, and red after film formation when the volume ratio is 8:1:2.
  • the size of the cellulose nanocrystals in the CNC suspension in step (1) is 100-400 nm in length and 20-50 nm in width.
  • the CNC suspension described in step (1) is prepared by the following method: mixing wood pulp or cellulose with concentrated sulfuric acid, heating under stirring conditions, adding water to terminate the reaction, centrifuging, dialysis to neutrality, and concentrating to obtain CNC suspension.
  • the concentration of the concentrated sulfuric acid is 60wt%-70wt%; the mass volume ratio of the wood pulp (absolutely dry wood pulp) or cellulose to the concentrated sulfuric acid is 1g:(8-10)/mL.
  • the rotational speed of the stirring is 300-400 rpm; the temperature of the heating treatment is 45-55° C., and the time of the heating treatment is 45-55 min.
  • the volume ratio of the concentrated sulfuric acid to water is 1:(10-15)10; the water here is the water for terminating the reaction.
  • the number of times of centrifugation is 3-4 times, the rotating speed of centrifugation is 8000-10000rpm, the time of centrifugation is 10-12min, and the temperature of centrifugation is 0-10°C.
  • the molecular weight cut-off of the dialysis bag is 12000-14000, and the dialysate is water.
  • the concentration is rotary steaming
  • the temperature of rotary steaming is 35-45° C.
  • the time of rotary steaming is 50-60 min.
  • the uniform mixing in step (1) refers to stirring treatment first, followed by ultrasonic treatment.
  • the time of the stirring treatment is 20 min, the rotating speed of the stirring treatment is 300-400 rpm, the time of the ultrasonic treatment is 5-10 min, and the ultrasonic frequency of the ultrasonic treatment is 20-40 KHz.
  • the lactic acid levorotatory, dextrorotatory and racemic lactic acid can be used.
  • the drying conditions in step (2) are that the temperature is 30-35° C., the ambient humidity is 50-60%, and the drying time is 3-5 days.
  • the drying is done in polystyrene petri dishes.
  • the present invention provides a wavelength-controllable cellulose iris film prepared by the above-mentioned preparation method.
  • the wavelength of the iris film of the present invention is between 450-650 nm, and different colors can be directly observed in the visible light range. Because it has different colors, and this color is produced by the internal structure, there is no disadvantage of dyeing and fading, and it can be used for color rendering in decoration.
  • the present invention has the following advantages and beneficial effects:
  • the selected raw materials of the present invention cellulose and lactic acid, all come from nature, and have the advantages of wide sources, low cost, good biocompatibility, etc.
  • the two raw materials are directly used for preparation without intermediate processes such as chemical synthesis. , which not only saves preparation time, but also achieves green environmental protection and no pollution;
  • the negative charge is introduced into the CNC prepared by hydrolysis of sulfuric acid, which is more conducive to the uniformity of the CNC suspension when it is dried to form a film.
  • the introduction of lactic acid in this system ensures the controllability of the reflection wavelength of the iris film;
  • the preparation method adopted in the present invention is an evaporation-induced self-assembly method, which is convenient to operate, simple to control conditions and good controllability;
  • the present invention realizes the controllable wavelength of different colors by adding lactic acid and glucose, and improves the brittleness of the pure CNC film at the same time; It has great application potential in packaging and optical electronic devices.
  • Fig. 1 is the lamellar distribution diagram of the cellulose iris film obtained in Example 1 under the scanning electron microscope;
  • Fig. 2 is the cellulose iridescent film that embodiment 1 makes observes the figure under the optical microscope;
  • Fig. 3 is the ultraviolet-visible light absorption spectrum of CNC mixed with lactic acid solution and glucose solution in different proportions in embodiment 1-5;
  • Fig. 4 is the ultraviolet-visible light absorption spectrum of different proportions of CNC and lactic acid solution mixed iris film in Comparative Examples 1-2;
  • Fig. 5 is the ultraviolet-visible light absorption spectrum of the iris film mixed with CNC and glucose solution in different proportions in Comparative Examples 3-4.
  • a preparation method of a wavelength-controllable cellulose iris film containing lactic acid solution and glucose solution comprising the following steps:
  • step (1) centrifuging the white milky solution described in step (1) at a speed of 10000r/min for 10min at 10°C, taking the upper suspension, centrifuging 3 times, and combining the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 45 °C, and the time of rotary steaming is 50min, obtains the high CNC solution of concentration;
  • a lactic acid solution with a concentration of 8wt% and a glucose solution with a concentration of 10wt% formulating a lactic acid solution with a concentration of 8wt% and a glucose solution with a concentration of 10wt%, the 3wt% CNC suspension obtained in step (4), the lactic acid solution of 8wt%, and the glucose solution of 10wt% are 12 by volume
  • the ratio of: 1:3 was mixed evenly, and then ultrasonically treated for 10min at an ultrasonic frequency of 40KHz, and the temperature was controlled at 10°C to obtain a CNC/lactic acid/glucose mixed solution;
  • step (6) Weigh 5 mL of the CNC/lactic acid/glucose mixture described in step (5), put it into a polystyrene petri dish, and dry it naturally for 72 hours at a temperature of 30°C and a humidity of 50% to obtain a CNC/lactic acid/glucose composite membrane , that is, the wavelength-controllable cellulose iris film.
  • a preparation method of a wavelength-controllable cellulose iris film containing lactic acid solution and glucose solution comprising the following steps:
  • step (1) centrifuging the white milky solution described in step (1) at a speed of 8000r/min for 12min at 0°C, taking the upper layer suspension, repeating the centrifugation 4 times, and combining the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 35 °C, and the time of rotary steaming is 60min, obtains the high CNC solution of concentration;
  • preparation concentration is the lactic acid solution of 9wt% and the glucose solution that concentration is 15wt%, the CNC suspension of 3wt% obtained by step (4) and the lactic acid solution of 9wt% and the 15wt% glucose solution are 11 by volume: Mix evenly at a ratio of 1:2, then ultrasonically treat for 10 minutes at an ultrasonic frequency of 20KHz, and control the temperature at 10°C to obtain a CNC/lactic acid/glucose solution mixture;
  • step (6) Weigh 5 mL of the CNC/lactic acid/glucose mixture described in step (5), put it into a polystyrene petri dish, and dry it naturally for 96h at a temperature of 35°C and a humidity of 60% to obtain a CNC/lactic acid/glucose composite membrane , that is, the wavelength-controllable cellulose iris film.
  • a preparation method of a wavelength-controllable cellulose iris film containing lactic acid solution and glucose solution comprising the following steps:
  • step (1) centrifuging the white milky solution described in step (1) at a speed of 10000r/min for 11min at 5°C, taking the upper layer suspension, repeating the centrifugation 3 times, and combining the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 40 DEG C, and the time of rotary steaming is 55min, to obtain the high CNC solution of concentration;
  • preparing a lactic acid solution with a concentration of 10wt% and a glucose solution with a concentration of 10wt%, the 4wt% CNC suspension obtained in step (4), the 10wt% lactic acid solution, and the 10wt% glucose solution are 10% by volume.
  • the ratio of :1:2 was mixed uniformly, and then ultrasonically treated at an ultrasonic frequency of 40KHz for 10 min, and the temperature was controlled at 10 °C to obtain a CNC/lactic acid/glucose mixed solution;
  • step (6) Weigh 5mL of the CNC/lactic acid/glucose mixture described in step (5) and put it into a polystyrene petri dish with a diameter of 35mm, and dry it naturally for 84h at a temperature of 30°C and a humidity of 60% to obtain CNC/lactic acid/glucose
  • the composite film is the wavelength-controllable cellulose iris film.
  • a preparation method of a wavelength-controllable cellulose iris film containing lactic acid solution and glucose solution comprising the following steps:
  • step (1) centrifuging the white milky solution described in step (1) at a speed of 8000r/min for 12min at 10°C, taking the upper layer suspension, repeating the centrifugation 3 times, and combining the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 40 DEG C, and the time of rotary steaming is 55min, to obtain the high CNC solution of concentration;
  • step (4) preparing a lactic acid solution with a concentration of 10wt% and a glucose solution with a concentration of 15wt%, the 3wt% CNC suspension obtained in step (4), the lactic acid solution of 10wt%, and the glucose solution of 15wt% are 9 by volume
  • the ratio of 1:2 was mixed evenly, and then ultrasonically treated for 8 minutes at an ultrasonic frequency of 40KHz, and the temperature was controlled at 10°C to obtain a CNC/lactic acid/glucose mixed solution;
  • step (6) Weigh 5 mL of the CNC/lactic acid/glucose mixture described in step (5) and put it into a polystyrene petri dish with a diameter of 35mm, and dry it naturally for 72h at a temperature of 30°C and a humidity of 55% to obtain CNC/lactic acid/glucose
  • the composite film is the wavelength-controllable cellulose iris film.
  • a preparation method of a wavelength-controllable cellulose iris film containing lactic acid solution and glucose solution comprising the following steps:
  • step (1) centrifuge the white milky solution described in step (1) at a speed of 10000r/min for 10min at 10°C, take the upper layer suspension, repeat the centrifugation 3 times, and combine the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 35 °C, and the time of rotary steaming is 55min, obtains the high CNC solution of concentration;
  • the ratio of: 1:2 was mixed evenly, and then ultrasonically treated for 5min at an ultrasonic frequency of 30KHz, and the temperature was controlled at 10°C to obtain a CNC/lactic acid/glucose mixed solution;
  • step (6) Weigh 5 mL of the CNC/lactic acid mixture described in step (5) and put it into a polystyrene petri dish with a diameter of 35 mm, and dry it naturally for 72 hours at a temperature of 35°C and a humidity of 55% to obtain a CNC/lactic acid/glucose composite membrane , that is, the wavelength-controllable cellulose iris film.
  • a kind of preparation method of the cellulose iris film containing lactic acid solution comprises the steps:
  • step (1) centrifuge the white milky solution described in step (1) at a speed of 10000r/min for 10min at 10°C, take the upper layer suspension, repeat the centrifugation 3 times, and combine the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 45 °C, and the time of rotary steaming is 50min, obtains the high CNC solution of concentration;
  • step (6) Weigh 5 mL of the CNC/lactic acid mixture described in step (5) and put it into a polystyrene petri dish with a diameter of 35 mm, and dry it naturally for 72 hours at a temperature of 30° C. and a humidity of 50% to obtain a CNC/lactic acid composite membrane, that is, The cellulose iridescent film.
  • a kind of preparation method of the cellulose iris film containing lactic acid solution comprises the steps:
  • step (1) centrifuging the white milky solution described in step (1) at a speed of 8000r/min for 12min at 0°C, taking the upper layer suspension, repeating the centrifugation 4 times, and combining the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 35 °C, and the time of rotary steaming is 60min, obtains the high CNC solution of concentration;
  • preparing a lactic acid solution with a concentration of 10 wt % mixing the 4 wt % CNC suspension obtained in step (4) with the 10 wt % lactic acid solution according to a volume ratio of 10:1, and then at an ultrasonic frequency of 20 KHz. Ultrasonic treatment was performed for 10 min, and the temperature was controlled at 10 °C to obtain a CNC/lactic acid solution mixture;
  • step (6) Weigh 5 mL of the CNC/lactic acid mixture described in step (5) and put it into a polystyrene petri dish with a diameter of 35 mm, and dry it naturally for 96 hours at a temperature of 35°C and a humidity of 60% to obtain a CNC/lactic acid composite membrane, that is, The cellulose iridescent film.
  • a preparation method of a wavelength-controllable cellulose iris film containing a glucose solution comprising the steps of:
  • step (1) centrifuge the white milky solution described in step (1) at a speed of 10000r/min for 10min at 10°C, take the upper layer suspension, repeat the centrifugation 3 times, and combine the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, and the temperature of rotary steaming is 45 °C, and the time of rotary steaming is 50min, obtains the high CNC solution of concentration;
  • step (4) preparing a glucose solution with a concentration of 15wt%, mixing the 3wt% CNC suspension obtained in step (4) and the 15wt% glucose solution according to a volume ratio of 11:2, and then at an ultrasonic frequency of 40KHz Ultrasonic treatment was carried out for 10 min, and the temperature was controlled at 10 °C to obtain a CNC/glucose mixture;
  • step (6) Weigh 5 mL of the CNC/glucose mixture described in step (5), put it into a polystyrene petri dish with a diameter of 35mm, and dry it naturally for 72h at a temperature of 30°C and a humidity of 50% to obtain a CNC/glucose composite membrane, namely The cellulose iridescent film.
  • a kind of preparation method of the cellulose iris film containing glucose solution comprises the steps:
  • step (1) centrifuging the white milky solution described in step (1) at a speed of 8000r/min for 12min at 0°C, taking the upper layer suspension, repeating the centrifugation 4 times, and combining the suspension;
  • step (3) pour the suspension described in step (2) into a dialysis bag with a molecular weight of 14,000, and dialyze with deionized water until the suspension is neutral;
  • step (3) the neutral suspension obtained in step (3) is concentrated by the method of rotary steaming, the temperature of rotary steaming is 35 °C, and the time of rotary steaming is 60min, obtains the high CNC solution of concentration;
  • step (4) preparing a glucose solution with a concentration of 10 wt %, mixing the 4 wt % CNC suspension obtained in step (4) with 10 wt % glucose solution according to a volume ratio of 10:2, and then ultrasonicating at an ultrasonic frequency of 40 KHz Treated for 10 min, the temperature was controlled at 10 °C to obtain a CNC/glucose solution mixture;
  • step (6) Weigh 5 mL of the CNC/glucose mixture described in step (5), put it into a polystyrene petri dish with a diameter of 35 mm, and dry it naturally for 96 h at a temperature of 35°C and a humidity of 60% to obtain a CNC/glucose composite membrane, namely The cellulose iridescent film.
  • Fig. 1 is the SEM image in Example 1, showing the obvious layered structure characteristics of the iris film
  • Fig. 2 is the imaging under the optical microscope in Example 1, showing the obvious birefringence phenomenon of the iris film
  • Fig. 3 is the implementation
  • the absorption wavelengths of the films formed in Examples 1 to 5 can be seen that the wavelengths of different proportions of CNC, lactic acid solution, and glucose solution are controlled in the visible light region, and the wavelengths are between 488-686 nm, corresponding to blue, green, and yellow respectively. , orange, and red five colors, which proves that the precise control of wavelengths in different color ranges can be achieved through this raw material ratio.
  • Comparative Example 1 and Comparative Example 2 are respectively glucose-free cellulose iridescent films prepared according to the method of proportioning the raw materials of CNC suspension and lactic acid solution in Example 2 and Example 3.
  • Figure 4 shows the UV-Vis absorption spectra of the iris films of CNC and lactic acid solutions in different proportions in Comparative Examples 1-2.
  • Figure 4 proves that the cellulose iridescent film prepared by adding only the CNC suspension and the lactic acid solution cannot achieve the control of different color wavelengths, both of which belong to the wavelengths in the green range.
  • Comparative Example 3 and Comparative Example 4 are lactic acid-free cellulose iridescent films prepared according to the method of proportioning the raw materials of CNC suspension and glucose solution in Example 2 and Example 3, respectively. Fig.
  • FIG. 5 is the ultraviolet-visible light absorption spectrum of the iris film mixed with CNC and glucose solution in different proportions in Comparative Examples 3-4.
  • Figure 5 proves that the cellulose iridescent film prepared by only adding CNC suspension and glucose solution cannot achieve the control of different color wavelengths, both of which belong to the wavelengths in the green range.

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Abstract

本发明属于功能膜材料的技术领域，公开了一种波长可控纤维素虹彩膜及其制备方法。方法：(1)将CNC悬浮液与乳酸溶液、葡萄糖溶液混合均匀，获得CNC/乳酸/葡萄糖混合液；所述CNC悬浮液为纤维素纳米晶悬浮液；(2)将CNC/乳酸/葡萄糖混合液进行干燥成膜，获得纤维素虹彩膜。本发明的方法简单、成本低。本发明通过添加乳酸和葡萄糖的方式，使得所制备的膜具有虹彩膜特征；而且虹彩膜的波长在可见光区，并实现了虹彩膜不同颜色波长可控。

Description

一种波长可控纤维素虹彩膜及其制备方法 技术领域
本发明属于功能膜材料的制备领域，具体涉及一种波长可控纤维素虹彩膜及其制备方法。
背景技术
纤维素作为组成植物细胞壁的主要成分，是自然界中分布最广、含量最高的一种可再生多糖，具有优异的生物相容性和生物降解性，因此被广泛于功能材料的制备和研究。
纤维素纳米晶(CNC)是指通过水解或酶解等方式除去天然纤维素纤维中的部分非结晶区域制备得到的高结晶度的棒状纳米级纤维素晶体，它具有高模量，高强度及高结晶度等特性，同时具有生物材料的轻质、无毒、可再生、可降解及生物相容性等优点。
硫酸水解法制备CNC，纤维素表面的羟基被转化为硫酸酯，引入了负表面电荷，进而形成稳定CNC的水分散体。CNC在一定浓度条件下自组装形成稳定的溶致手性向列结构，由于其具有优异的光学特性，被广泛应用在防伪材料、感应器和光学器件中。
纯CNC制备的虹彩膜，具有脆性大，波长受外部条件影响大而不易控制等缺点，这严重影响了CNC虹彩膜的实用性。在专利申请(申请号CN201080019562.0)“纳米晶纤维素膜虹彩波长的控制”中采用了一种纯机械能输入的方法，获得期望或预定的虹彩波长。这虽然在一定程度上实现了波长可控，但纯机械能输入的方法耗能高、成本较大，并不适合企业的大规模生产。
发明内容
为了克服现有技术存在的上述不足，本发明的目的是提供一种波长可控纤维素虹彩膜及其制备方法。本发明通过添加乳酸和葡萄糖的方式，实现了不同颜色波长可控，同时改善纯CNC膜的脆性。
本发明的目的通过如下技术方案实现：
一种波长范围可控纤维素虹彩膜的制备方法，包括如下步骤：
(1)将CNC悬浮液与乳酸溶液、葡萄糖溶液混合均匀，获得CNC/乳酸/葡萄糖混合液；所述CNC悬浮液为纤维素纳米晶悬浮液，
(2)将CNC/乳酸/葡萄糖混合液进行干燥成膜，获得纤维素虹彩膜。
步骤(1)中所述CNC悬浮液与乳酸溶液、葡萄糖溶液的体积比为(12-8)：1：(2-3)；
步骤(1)中所述CNC悬浮液中纤维素纳米晶的浓度为3-4wt％；
所述乳酸溶液的浓度为8-10wt％；葡萄糖溶液的浓度为10-20wt％；
乳酸溶液的溶剂为水；葡萄糖溶液的溶剂为水。
所述CNC溶液与乳酸溶液、葡萄糖溶液的体积比为12:1:3时，成膜后显示蓝色、体积比为11:1:2时，成膜后显示绿色、体积比为10:1:2，成膜后显示黄色、9:1:2时，成膜后显示橙色，体积比为8:1:2时，成膜后显示红色。
步骤(1)中所述CNC悬浮液中纤维素纳米晶的尺寸为长100-400nm，宽20-50nm。
步骤(1)中所述CNC悬浮液通过以下方法制备得到：将木浆或纤维素与浓硫酸混合，在搅拌的条件下加热处理，加入水终止反应，离心，透析至中性，浓缩，获得CNC悬浮液。
所述浓硫酸的浓度为60wt％-70wt％；所述木浆(绝干木浆)或纤维素与浓硫酸的质量体积比为1g:(8-10)/mL。
所述搅拌的转速为300-400rpm；所述加热处理的温度为45-55℃，所述加热处理的时间为45-55min。
所述浓硫酸与水的体积比为1：(10～15)10；此处的水为终止反应的水。
所述离心的次数为3-4次，离心的转速为8000-10000rpm，离心的时间为10-12min，离心的温度为0-10℃。
所述透析袋的截留分子量为12000～14000，透析液为水。
所述浓缩为旋蒸，旋蒸的温度为35-45℃，旋蒸时间为50-60min。
步骤(1)中所述混合均匀是指先搅拌处理，后超声处理。
所述搅拌处理的时间为20min，搅拌处理的转速为300-400rpm，超声处理的时间为5-10min，超声处理的超声频率为20-40KHz。
所述乳酸：左旋、右旋以及外消旋体的乳酸都可以。
步骤(2)中所述干燥的条件为温度为30-35℃，环境湿度50-60％，干燥的时间为3-5天。
所述干燥在聚苯乙烯培养皿中干燥。
本发明提供一种由上述的制备方法制得的波长可控纤维素虹彩膜。本发明的虹彩膜波长在450-650nm之间，用可见光范围内可以直接观察到不同的颜色。因为具有不同的颜色，而且这种颜色是由内部结构产生的，没有染料染色会掉色的缺点，可以用在装饰方面做色彩的渲染。
与现有技术相比，本发明具有如下优点和有益效果：
(1)本发明所选用的原料纤维素和乳酸，都来自于自然界中，且具有来源广，成本低，生物相容性好等优点，两种原料直接用于制备，无需化学合成等中间过程，既节省制备时间又可达到绿色环保无污染；
(2)经硫酸水解制备的CNC中引入了负电荷，更有利于CNC悬浮液干燥成膜时的均匀性，在这体系中引入乳酸，使虹彩膜反射波长的可控性得到了保证；
(3)本发明采用的制备方法是蒸发诱导自组装方式，操作方便，条件操控简单，可控性好；
(4)本发明通过添加乳酸和葡萄糖的方式，实现了不同颜色波长可控，同时改善纯CNC膜的脆性；本发明所制备的膜具有虹彩膜特征，而且膜的波长在可见光区，在装饰包装、光学电子器件方面有较大的的应用潜能。
附图说明
图1为实施例1制得的纤维素虹彩膜在扫描电镜下的层状分布图；
图2为实施例1制得的纤维素虹彩膜在光学显微镜下观察图；
图3为实施例1-5中不同比例的CNC与乳酸溶液、葡萄糖溶液混合虹彩膜紫外-可见光吸收光谱；
图4为对比例1-2中不同比例的CNC与乳酸溶液混合虹彩膜紫外-可见光吸收光谱；
图5为对比例3-4中不同比例的CNC与葡萄糖溶液混合虹彩膜紫外-可见光吸收光谱。
具体实施方式
以下结合附图和实例对本发明的具体实施作进一步说明，但本发明的实施和保护不限于此。需指出的是，以下若有未特别详细说明之过程，均是本领域技术人员可参照现有技术实现或理解的。所用试剂或仪器未注明生产厂商者，视为可以通过市售购买得到的常规产品。
实施例1
一种含乳酸溶液和葡萄糖溶液的波长可控纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与混合200ml浓度为60wt％的浓硫酸溶液，在50℃下以400r/min转速搅拌50min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在10℃下以10000r/min的速度离心10min，取上层悬浮液，离心3次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为45℃，旋蒸的时间为50min，得到浓度高的CNC溶液；
(5)配制浓度为8wt％的乳酸溶液和浓度为10wt％的葡萄糖溶液，将步骤(4)得到的3wt％的CNC悬浮液与8wt％的乳酸溶液、10wt％的葡萄糖溶液按照体积比为12:1:3的比例混合均匀，然后在超声频率为40KHz下超声处理10min，温度控制在10℃，得到CNC/乳酸/葡萄糖混合液；
(6)称取5mL步骤(5)所述CNC/乳酸/葡萄糖混合液放入聚苯乙烯培养皿中，在温度为30℃湿度为50％下自然干燥72h，得到CNC/乳酸/葡萄糖复合膜，即所述波长可控纤维素虹彩膜。
实施例2
一种含乳酸溶液和葡萄糖溶液的波长可控纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与160ml浓度为70wt％的浓硫酸溶液，在45℃下以300r/min转速搅拌55min，加入浓硫酸溶液10倍体积的去离子水终止反 应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在0℃下以8000r/min的速度离心12min，取上层悬浮液，重复离心4次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为35℃，旋蒸的时间为60min，得到浓度高的CNC溶液；
(5)配制浓度为9wt％的乳酸溶液和浓度为15wt％的葡萄糖溶液，将步骤(4)得到的3wt％的CNC悬浮液与9wt％的乳酸溶液和15wt％葡萄糖溶液按照体积比为11:1:2的比例混合均匀，然后在超声频率为20KHz下超声处理10min，温度控制在10℃，得到CNC/乳酸/葡萄糖溶液混合液；
(6)称取5mL步骤(5)所述CNC/乳酸/葡萄糖混合液放入聚苯乙烯培养皿中，在温度为35℃湿度为60％下自然干燥96h，得到CNC/乳酸/葡萄糖复合膜，即所述波长可控纤维素虹彩膜。
实施例3
一种含乳酸溶液和葡萄糖溶液的波长可控纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与180ml浓度为64wt％的浓硫酸溶液混合，在55℃下以350r/min转速搅拌45min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在5℃下以10000r/min的速度离心11min，取上层悬浮液，重复离心3次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为40℃，旋蒸的时间为55min，得到浓度高的CNC溶液；
(5)配制浓度为10wt％的乳酸溶液和浓度为10wt％的葡萄糖溶液，将步骤(4)得到的4wt％的CNC悬浮液和10wt％的乳酸溶液、10wt％的葡萄糖溶液按照体积比为10:1:2的比例混合均匀，然后在超声频率为40KHz下超声处理10 min，温度控制在10℃，得到CNC/乳酸/葡萄糖混合液；
(6)称取5mL步骤(5)所述CNC/乳酸/葡萄糖混合液放入直径35mm聚苯乙烯培养皿中，在温度为30℃湿度为60％下自然干燥84h，得到CNC/乳酸/葡萄糖复合膜，即所述波长可控纤维素虹彩膜。
实施例4
一种含乳酸溶液和葡萄糖溶液的波长可控纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与180ml浓度为64wt％的浓硫酸溶液混合，在55℃下以400r/min转速搅拌45min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在10℃下以8000r/min的速度离心12min，取上层悬浮液，重复离心3次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为40℃，旋蒸的时间为55min，得到浓度高的CNC溶液；
(5)配制浓度为10wt％的乳酸溶液和浓度为15wt％的葡萄糖溶液，将步骤(4)得到的3wt％的CNC悬浮液与10wt％的乳酸溶液、15wt％的葡萄糖溶液按照体积比为9:1:2的比例混合均匀，然后在超声频率为40KHz下超声处理8min，温度控制在10℃，得到CNC/乳酸/葡萄糖混合液；
(6)称取5mL步骤(5)所述CNC/乳酸/葡萄糖混合液放入直径35mm聚苯乙烯培养皿中，在温度为30℃湿度为55％下自然干燥72h，得到CNC/乳酸/葡萄糖复合膜，即所述波长可控纤维素虹彩膜。
实施例5
一种含乳酸溶液和葡萄糖溶液的波长可控纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与200ml浓度为60wt％的浓硫酸溶液混合，在55℃下以400r/min转速搅拌50min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在10℃下以10000r/min的速度离心10min，取上层悬浮液，重复离心3次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为35℃，旋蒸的时间为55min，得到浓度高的CNC溶液；
(5)配制浓度为10wt％的乳酸溶液和浓度为20wt％的葡萄糖溶液，将步骤(4)得到的4wt％的CNC悬浮液与10wt％的乳酸溶液、20wt％的葡萄糖溶液按照体积比为8:1:2的比例混合均匀，然后在超声频率为30KHz下超声处理5min，温度控制在10℃，得到CNC/乳酸/葡萄糖混合液；
(6)称取5mL步骤(5)所述CNC/乳酸混合液放入直径35mm聚苯乙烯培养皿中，在温度为35℃湿度为55％下自然干燥72h，得到CNC/乳酸/葡萄糖复合膜，即所述波长可控纤维素虹彩膜。
对比例1
一种含乳酸溶液的纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与200ml浓度为60wt％的浓硫酸溶液混合，在50℃下以400r/min转速搅拌50min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在10℃下以10000r/min的速度离心10min，取上层悬浮液，重复离心3次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为45℃，旋蒸的时间为50min，得到浓度高的CNC溶液；
(5)配制浓度为9wt％的乳酸溶液，将步骤(4)得到的3wt％的CNC悬浮液与9wt％的乳酸溶液按照体积比为11:1的比例混合均匀，然后在超声频率为40KHz下超声处理10min，温度控制在10℃，得到CNC/乳酸混合液；
(6)称取5mL步骤(5)所述CNC/乳酸混合液放入直径35mm聚苯乙烯 培养皿中，在温度为30℃湿度为50％下自然干燥72h，得到CNC/乳酸复合膜，即所述纤维素虹彩膜。
对比例2
一种含乳酸溶液溶液的纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与160ml浓度为70wt％的浓硫酸溶液混合，在45℃下以300r/min转速搅拌55min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在0℃下以8000r/min的速度离心12min，取上层悬浮液，重复离心4次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为35℃，旋蒸的时间为60min，得到浓度高的CNC溶液；
(5)配制浓度为10wt％的乳酸溶液，将步骤(4)得到的4wt％的CNC悬浮液与10wt％的乳酸溶液按照体积比为10:1的比例混合均匀，然后在超声频率为20KHz下超声处理10min，温度控制在10℃，得到CNC/乳酸溶液混合液；
(6)称取5mL步骤(5)所述CNC/乳酸混合液放入直径35mm聚苯乙烯培养皿中，在温度为35℃湿度为60％下自然干燥96h，得到CNC/乳酸复合膜，即所述纤维素虹彩膜。
对比例3
一种含葡萄糖溶液的波长可控纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与200ml浓度为60wt％的浓硫酸溶液混合，在50℃温度下以400r/min转速搅拌50min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在10℃下以10000r/min的速度离心10min，取上层悬浮液，重复离心3次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温 度为45℃，旋蒸的时间为50min，得到浓度高的CNC溶液；
(5)配制浓度为15wt％的葡萄糖溶液，将步骤(4)得到的3wt％的CNC悬浮液与15wt％的葡萄糖溶液按照体积比为11:2的比例混合均匀，然后在超声频率为40KHz下超声处理10min，温度控制在10℃，得到CNC/葡萄糖混合液；
(6)称取5mL步骤(5)所述CNC/葡萄糖混合液放入直径35mm聚苯乙烯培养皿中，在温度为30℃湿度为50％下自然干燥72h，得到CNC/葡萄糖复合膜，即所述纤维素虹彩膜。
对比例4
一种含葡萄糖溶液的纤维素虹彩膜的制备方法，包括如下步骤：
(1)将绝干针叶木浆20g与160ml浓度为70wt％的浓硫酸溶液混合，在45℃下以300r/min转速搅拌55min，加入浓硫酸溶液10倍体积的去离子水终止反应，得到白色乳状溶液；
(2)将步骤(1)所述白色乳状溶液在0℃下以8000r/min的速度离心12min，取上层悬浮液，重复离心4次，合并悬浮液；
(3)将步骤(2)所述悬浮液倒入分子量14000的透析袋中，用去离子水透析，直至悬浮液呈中性；
(4)将步骤(3)得到的中性悬浮液采用旋蒸的方法进行浓缩，旋蒸的温度为35℃，旋蒸的时间为60min，得到浓度高的CNC溶液；
(5)配制浓度为10wt％的葡萄糖溶液，将步骤(4)得到的4wt％的CNC悬浮液与10wt％葡萄糖溶液按照体积比为10:2的比例混合均匀，然后在超声频率为40KHz下超声处理10min，温度控制在10℃，得到CNC/葡萄糖溶液混合液；
(6)称取5mL步骤(5)所述CNC/葡萄糖混合液放入直径35mm聚苯乙烯培养皿中，在温度为35℃湿度为60％下自然干燥96h，得到CNC/葡萄糖复合膜，即所述纤维素虹彩膜。
上述实施例1～5所成的膜都表现出较强的虹彩膜特征。图1是实施例1中的SEM图，表现出虹彩膜明显的层状结构特征，图2是实施例1中的光学显微镜下的成像，表现出虹彩膜明显的双折射现象，图3是实施例1～5所成膜的吸 收波长，可以看出，不同比例CNC和乳酸溶液、葡萄糖溶液混合的波长都控制在可见光区，并且将波长在488-686nm之间，分别对应蓝、绿、黄、橙、红五种颜色，证明了通过这种原料配比可实现精准控制不同颜色范围内的波长。对比例1和对比例2分别是按照实施例2和实施例3的CNC悬浮液和乳酸溶液原料配比的方法制备的不含葡萄糖的纤维素虹彩膜。图4为对比例1-2中不同比例的CNC与乳酸溶液混合虹彩膜紫外-可见光吸收光谱。图4证明了只添加CNC悬浮液和乳酸溶液制备的纤维素虹彩膜并不能实现不同颜色波长的控制，这两个对比例同属于绿色范围内的波长。对比例3和对比例4分别是按照实施例2和实施例3的CNC悬浮液和葡萄糖溶液原料配比的方法制备的不含乳酸的纤维素虹彩膜。图5为对比例3-4中不同比例的CNC与葡萄糖溶液混合虹彩膜紫外-可见光吸收光谱。图5证明了只添加CNC悬浮液和葡萄糖溶液制备的纤维素虹彩膜并不能实现不同颜色波长的控制，这两个对比例同属于绿色范围内的波长。
以上实施例仅为本发明较优的实施方式，仅用于解释本发明，而非限制本发明，本领域技术人员在未脱离本发明精神实质下所作的改变、替换、修饰等均应属于本发明的保护范围。

Claims (10)

  1. 一种波长可控纤维素虹彩膜的制备方法，其特征在于：包括如下步骤：
    (1)将CNC悬浮液与乳酸溶液、葡萄糖溶液混合均匀，获得CNC/乳酸/葡萄糖混合液；所述CNC悬浮液为纤维素纳米晶悬浮液；
    (2)将CNC/乳酸/葡萄糖混合液进行干燥成膜，获得纤维素虹彩膜。
  2. 根据权利要求1所述波长范围可控纤维素虹彩膜的制备方法，其特征在于：步骤(1)中所述CNC悬浮液与乳酸溶液、葡萄糖溶液的体积比为(12-8)：1：(2-3)；
    步骤(1)中所述CNC悬浮液中纤维素纳米晶的浓度为3-4wt％；
    所述乳酸溶液的浓度为8-10wt％；葡萄糖溶液的浓度为10-20wt％。
  3. 根据权利要求1所述波长可控纤维素虹彩膜的制备方法，其特征在于：乳酸溶液的溶剂为水；葡萄糖溶液的溶剂为水；
    所述CNC溶液与乳酸溶液、葡萄糖溶液的体积比为12:1:3时，成膜后显示蓝色；体积比为11:1:2时，成膜后显示绿色；体积比为10:1:2，成膜后显示黄色；9:1:2时，成膜后显示橙色；体积比为8:1:2时，成膜后显示红色。
  4. 根据权利要求1所述波长可控纤维素虹彩膜的制备方法，其特征在于：步骤(1)中所述CNC悬浮液中纤维素纳米晶的尺寸为长100-400nm，宽20-50nm；
    步骤(2)中所述干燥的条件为温度为30-35℃，环境湿度50-60％，干燥的时间为3-5天。
  5. 根据权利要求1所述波长可控纤维素虹彩膜的制备方法，其特征在于：步骤(1)中所述CNC悬浮液通过以下方法制备得到：将木浆或纤维素与浓硫酸混合，在搅拌的条件下加热处理，加入水终止反应，离心，透析至中性，浓缩，获得CNC悬浮液。
  6. 根据权利要求5所述波长可控纤维素虹彩膜的制备方法，其特征在于：所述浓硫酸的浓度为60wt％-70wt％；所述木浆或纤维素与浓硫酸的质量体积比为1g:(8-10)/mL；
    所述搅拌的转速为300-400rpm；所述加热处理的温度为45-55℃，所述加热处理的时间为45-55min。
  7. 根据权利要求5所述波长可控纤维素虹彩膜的制备方法，其特征在于： 所述浓硫酸与水的体积比为1：(10～15)10；此处的水为终止反应的水；
    所述透析袋的截留分子量为12000～14000，透析液为水；
    所述离心的次数为3-4次，离心的转速为8000-10000rpm，离心的时间为10-12min，离心的温度为0-10℃；
    所述浓缩为旋蒸，旋蒸的温度为35-45℃，旋蒸时间为50-60min。
  8. 根据权利要求5所述波长可控纤维素虹彩膜的制备方法，其特征在于：步骤(1)中所述混合均匀是指先搅拌处理，后超声处理。
  9. 根据权利要求8所述波长可控纤维素虹彩膜的制备方法，其特征在于：混合均匀中，所述搅拌处理的时间为15～30min，搅拌处理的转速为300-400rpm，超声处理的时间为5-10min，超声处理的超声频率为20-40KHz。
  10. 一种由权利要求1～9任一项所述制备方法得到的波长可控纤维素虹彩膜。
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