Transparent hydrophobic paper as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of hydrophobic materials, and particularly relates to transparent hydrophobic paper and a preparation method and application thereof.The preparation method comprises the steps that a reaction reagent n-decanoic acid is mixed with a catalyst, a condensing agent and an organic solvent to obtain a reaction solution, the catalyst is 4-dimethylaminopyridine, and the condensing agent is 4-dimethylaminopyridine; the condensing agent is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, and the solvent is a solvent; the transparent paper-based material is placed in a reaction solution to be subjected to esterification reaction, and the transparency of the transparent paper-based material is hardly influenced; the esterification reaction introduces a hydrophobic alkyl chain on the surface of the paper-based material, so that the hydrophobicity of the paper-based material is improved, the transparency of the paper-based material can be retained, and the film-forming property of PEDOT: PSS on a paper base is not influenced.

Description

Technical Field

[0001] The present application relates to the technical field of hydrophobic materials, and more specifically, to a transparent hydrophobic paper and a preparation method and application thereof. Background Art

[0002] As an environmentally friendly material, paper has broad application prospects in the fields of flexible electronics, optoelectronic devices, sensors, etc. At present, PEDOT:PSS (including poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(4-styrenesulfonic acid) (PSS)) is regarded as one of the ideal materials for flexible electronic devices due to its excellent flexible conductive properties. It is usually prepared by solution spin coating. However, traditional transparent paper substrates have strong hydrophilicity. When the PEDOT:PSS aqueous solution is spin-coated on its surface, it is easy to cause paper deformation, thereby affecting the performance of the device. Summary of the invention

[0003] The present application is provided to solve the above defects existing in the prior art. A transparent hydrophobic paper and its preparation method and application are needed, which can improve the hydrophobicity of the paper-based material, maintain its transparency, and do not affect the film-forming property of PEDOT:PSS on the paper-based material, thereby improving the application performance of the paper-based material in electronic devices.

[0004] In a first aspect of the present application, a method for preparing a transparent hydrophobic paper is provided, the method comprising: mixing a reaction reagent, n-decanoic acid, a catalyst, a condensing agent and an organic solvent to obtain a reaction solution, wherein the catalyst is 4-dimethylaminopyridine, and the condensing agent is 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride; placing a transparent paper base material in the reaction solution, causing an esterification reaction, and obtaining the transparent hydrophobic paper.

[0005] In a second aspect of the present application, there is provided a transparent hydrophobic paper prepared by the preparation method described in any embodiment of the present application.

[0006] The third aspect of the present application provides an application of the transparent hydrophobic paper described in any embodiment of the present application in an electronic device.

[0007] The transparent hydrophobic paper and its preparation method and application provided in each embodiment of the present application can promote the esterification reaction between decanoic acid and paper-based materials through catalysts and condensation agents, so that after the esterification reaction, hydrophobic alkyl chains are introduced on the surface of the transparent paper-based material to improve its hydrophobicity and retain its transparency without affecting the film-forming property of PEDOT:PSS on the paper base; the application performance of transparent hydrophobic paper in the fields of flexible electronics, optoelectronic devices, sensors, etc. can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In the drawings, which are not necessarily drawn to scale, the same reference numerals may describe similar parts in different views. The same reference numerals with letter suffixes or different letter suffixes may represent different instances of similar parts. The accompanying drawings generally illustrate various embodiments by way of example and not limitation, and together with the specification and claims, are used to illustrate the embodiments applied for. When appropriate, the same reference numerals are used throughout the drawings to refer to the same or similar parts. Such embodiments are illustrative and are not intended to be exhaustive or exclusive embodiments of the present apparatus or method.

[0009] Figure 1 The contact angle result graphs of the transparent hydrophobic paper prepared according to Example 1 of the present application are shown, wherein (a) is the contact angle result graph of the glass paper before the esterification reaction, and (b) is the contact angle result graph of the transparent hydrophobic paper obtained after the esterification reaction; Figure 2 SEM images of the transparent hydrophobic paper prepared according to Example 1 of the present application and the cellophane before the esterification reaction are shown, wherein (a) is the SEM image of the cellophane before the esterification reaction, and (b) is the SEM image of the transparent hydrophobic paper obtained after the esterification reaction; Figure 3 Graphs showing contact angle results of transparent hydrophobic paper prepared according to different embodiments of the present application; Figure 4 The following are the physical pictures of the transparent hydrophobic paper after spin coating with PEDOT:PSS aqueous solution according to Example 1 of the present application, wherein (a) is a physical picture of the transparent hydrophobic paper placed on a table, and (b) is a physical picture of the transparent hydrophobic paper in a light-transmitting state; Figure 5 A comparison chart of the light transmittance of the transparent hydrophobic paper after spin coating according to Example 5 of the present application is shown. DETAILED DESCRIPTION

[0010] In order to enable those skilled in the art to better understand the technical solution of the present application, the present application is described in detail below in conjunction with the accompanying drawings and specific implementation methods. The embodiments of the present application are further described in detail below in conjunction with the accompanying drawings and specific implementation methods, but are not intended to limit the present application.

[0011] The words "first", "second" and similar words used in this application do not indicate any order, quantity or importance, but are only used to distinguish. The words "include" or "comprise" and similar words mean that the elements before the word include the elements listed after the word, and do not exclude the possibility of including other elements.

[0012] According to an embodiment of the present application, a method for preparing a transparent hydrophobic paper is provided, the method comprising: mixing a reaction reagent, n-decanoic acid, a catalyst, a condensing agent and an organic solvent to obtain a reaction solution, the catalyst being 4-dimethylaminopyridine, and the condensing agent being 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride; placing a transparent paper base material in the reaction solution, causing an esterification reaction, and obtaining the transparent hydrophobic paper.

[0013] Taking cellophane as an example, the esterification reaction mechanism is as follows: .

[0014] During the reaction, the hydroxyl groups of the cellophane and the hydroxyl groups of the carboxylic acid of the decanoic acid undergo an esterification reaction to reduce water and obtain transparent hydrophobic paper. The catalyst and condensation agent can promote the esterification reaction of the bacterial cellulose paper and the decanoic acid at room temperature. The hydrophobic alkyl chains are introduced to the surface of the bacterial cellulose paper, which improves the hydrophobicity of the paper base and ensures that the transparency is almost unaffected. It also does not affect the film-forming property of PEDOT:PSS on the paper base.

[0015] In some embodiments, the molar ratio of n-decanoic acid, 4-dimethylaminopyridine and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:1:1-1.5. The addition amount of catalyst and condensing agent relative to the molar amount of n-decanoic acid can improve the progress of the esterification reaction.

[0016] In some embodiments, the organic solvent is dichloromethane.

[0017] In some embodiments, the concentration of n-decanoic acid in the reaction solution is 6-15 g / L; preferably, the concentration of n-decanoic acid in the reaction solution is 12-13 g / L. For example, the concentration of n-decanoic acid in the reaction solution is 12.5 g / L.

[0018] In some embodiments, the temperature of the esterification reaction of the transparent paper-based material is room temperature, and the reaction time is 4-12 hours; preferably, the reaction time is 4-8 hours, so as to ensure the esterification process of the bacterial cellulose paper in the reaction solution and affect the performance of the paper.

[0019] In some embodiments, the transparent paper-based material is cellulose paper, which contains cellulose components, such as glass paper and bacterial cellulose paper.

[0020] In some embodiments, the structural formula of the cellulose is as shown in Formula I: (I).

[0021] In some embodiments, the preparation method further comprises: the paper-based material undergoes an esterification reaction and then is dried at room temperature to obtain the transparent hydrophobic paper.

[0022] According to an embodiment of the present application, a transparent hydrophobic paper prepared by the preparation method described in any embodiment of the present application is also provided. The transparent hydrophobic paper obtained after the esterification reaction has a contact angle with water increased from the original 22° to 80°.

[0023] According to an embodiment of the present application, there is also provided an application of the transparent hydrophobic paper described in any embodiment of the present application in an electronic device.

[0024] According to an embodiment of the present application, a conductive paper for an electronic device is further provided, wherein the conductive paper comprises the transparent hydrophobic paper described in any embodiment of the present application and a PEDOT:PSS film on the transparent hydrophobic paper.

[0025] According to an embodiment of the present application, a method for preparing conductive paper for electronic devices is also provided, the preparation method comprising: spin coating a PEDOT:PSS aqueous solution on the transparent hydrophobic paper described in any embodiment of the present application. In some embodiments, the mass concentration of the solid solution of the PEDOT:PSS aqueous solution is 1.3%-1.7%.

[0026] Example 1 Weigh n-decanoic acid, 4-dimethylaminopyridine, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride in a molar ratio of 1:1:1.2, add dichloromethane into a beaker, pour the weighed 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride into it, wait until it is completely dissolved in dichloromethane (the volume of dichloromethane is 80 ml), then add the weighed n-decanoic acid and 4-dimethylaminopyridine, stir at room temperature until the reaction solution is clear, and the concentration of n-decanoic acid in the reaction solution is 12.5 g / L.

[0027] After cutting the cellophane into appropriate sizes, place it in the reaction solution for 4 h. After the reaction is completed, take out the paper-based material, rinse it with dichloromethane, and dry it naturally at room temperature.

[0028] The transparent hydrophobic paper obtained in Example 1 and the glassine paper before esterification were respectively tested for contact angle using a fully automatic video optical contact angle measuring instrument to obtain the following: Figure 1 The results shown by Figure 1 It can be seen that after the introduction of the hydrophobic alkyl chain, the hydrophilicity of the cellophane paper changes to a suitable hydrophobicity. The contact angle between the cellophane paper and water increases from the original 22° to 80°. Therefore, the transparent hydrophobic paper prepared in the present application has a suitable hydrophobicity.

[0029] The transparent hydrophobic paper obtained in Example 1 and the glassine paper before esterification were detected by SEM scanning electron microscope, respectively, and the following results were obtained: Figure 2 The results shown by Figure 2It can be seen that the surface of the cellophane paper changes from rough to smooth after the introduction of the hydrophobic alkyl chains. Therefore, the surface of the bacterial cellulose paper changes by introducing the hydrophobic alkyl chains.

[0030] Example 2 Weigh n-decanoic acid, 4-dimethylaminopyridine, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride in a molar ratio of 1:1:1, add dichloromethane into a beaker, pour in the weighed 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, wait until it is completely dissolved in dichloromethane (the volume of dichloromethane is 80 ml), then add the weighed n-decanoic acid and 4-dimethylaminopyridine, and stir at room temperature until the reaction solution is clear.

[0031] After cutting the cellophane into appropriate sizes, place it in the reaction solution for 4 hours. After the reaction is completed, take out the paper-based material, rinse it with dichloromethane, and dry it naturally at room temperature.

[0032] The transparent hydrophobic paper obtained in Example 2 and the cellophane before esterification were tested for contact angle using a fully automatic video optical contact angle measuring instrument, and it was found that after the introduction of the hydrophobic alkyl chain, the transparent hydrophobic paper changed from hydrophilic to hydrophobic. The contact angle of the cellophane with water increased from 22° to 56°.

[0033] Example 3 Compared with Example 1, the time for placing the cellophane in the reaction solution for esterification reaction was changed to 2 h, 6 h and 8 h, and the other steps were the same as Example 1.

[0034] Example 4 Compared with Example 1, the cellophane was replaced by bacterial cellulose paper, and the time for which the bacterial cellulose paper was placed in the reaction solution for the esterification reaction was changed to 2 h, 6 h, 8 h and 10 h respectively. The other steps were the same as in Example 1.

[0035] The contact angle results obtained in Example 3 and Example 4 are as follows Figure 3 As shown, through Figure 3 It can be found that the contact angle of cellophane and bacterial cellulose paper does not change much after the esterification reaction time is 4h, that is, more than 4h.

[0036] Comparative Example Weigh n-decanoic acid and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride in a molar ratio of 1:1.2, add dichloromethane into a beaker, pour in the weighed 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and when it is completely dissolved in dichloromethane (the volume of dichloromethane is 80 ml), add the weighed n-decanoic acid and stir at room temperature until the reaction solution is clear.

[0037] After cutting the cellophane into appropriate sizes, place it in the reaction solution for 4 h. After the reaction is completed, take out the paper-based material, rinse it with dichloromethane, and dry it naturally at room temperature.

[0038] The contact angle of the cellophane obtained in the comparative example was tested and found to have little change, indicating that the hydrophobic alkyl chain was not successfully introduced into the cellophane.

[0039] Example 5 The PEDOT:PSS aqueous solution was spin-coated on the glass paper before esterification treatment and the obtained transparent hydrophobic paper in Example 1, and the bacterial cellulose paper before esterification treatment and the obtained transparent hydrophobic paper in Example 4. The mass concentration of the solid solution in the PEDOT:PSS aqueous solution was 1.3-1.7%. The actual picture of the transparent hydrophobic paper after spin coating in Example 1 is as follows: Figure 4 As shown, through Figure 4 The transparent hydrophobic paper can be obtained without deformation and has the characteristic of light transmission.

[0040] The transmittance of the spin-coated paper is shown in Figure 5 As shown, Figure 5 From left to right in the figure are bacterial cellulose paper before esterification, bacterial cellulose paper after esterification, glass paper before esterification, glass paper after esterification, bacterial cellulose paper after esterification and spin coating with PEDOT:PSS, and glass paper after esterification and spin coating with PEDOT:PSS. Figure 5 It can be seen that the transmittance of the transparent hydrophobic paper does not change substantially before and after the esterification reaction. The PEDOT:PSS aqueous solution can form a film on the transparent hydrophobic paper obtained in the present application, and the transparent hydrophobic paper will not deform, thereby avoiding affecting the performance of the electronic device.

[0041] In addition, although exemplary embodiments have been described herein, the scope includes any and all embodiments based on the present application with equivalent elements, modifications, omissions, combinations (e.g., various embodiments intersecting schemes), adaptations or changes. The elements in the claims are to be interpreted broadly based on the language adopted in the claims, and are not limited to the examples described in this specification or during the practice of this application, and the examples are to be interpreted as non-exclusive. Therefore, this specification and examples are intended to be considered as examples only, and the true scope and spirit are indicated by the following claims and the full scope of their equivalents.

[0042] The above description is intended to be illustrative rather than restrictive. For example, the above examples (or one or more schemes thereof) may be used in combination with each other. For example, a person of ordinary skill in the art may use other embodiments when reading the above description. In addition, in the above-mentioned specific embodiments, various features may be grouped together to simplify the present application. This should not be interpreted as an intention that a feature of an application that does not require protection is necessary for any claim. On the contrary, the subject matter of the present application may be less than all the features of an embodiment of a particular application. Thus, the following claims are incorporated herein in the specific embodiments as examples or embodiments, wherein each claim is independently a separate embodiment, and it is considered that these embodiments may be combined with each other in various combinations or arrangements. The scope of the present invention should be determined with reference to the appended claims and the full scope of equivalent forms granted by these claims.

[0043] The above embodiments are only exemplary embodiments of the present application and are not intended to limit the present invention. The protection scope of the present invention is defined by the claims. Those skilled in the art may make various modifications or equivalent substitutions to the present invention within the essence and protection scope of the present application, and such modifications or equivalent substitutions shall also be deemed to fall within the protection scope of the present invention.

Claims

1. A method for preparing a transparent hydrophobic paper, characterized in that: The preparation method comprises: mixing a reaction reagent, n-decanoic acid, a catalyst, a condensing agent and an organic solvent to obtain a reaction solution, wherein the catalyst is 4-dimethylaminopyridine and the condensing agent is 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride; placing a transparent paper base material in the reaction solution to cause an esterification reaction to obtain a transparent hydrophobic paper.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the n-decanoic acid, 4-dimethylaminopyridine and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:1:1-1.

5.

3. The preparation method according to claim 1, characterized in that: The organic solvent is dichloromethane.

4. The preparation method according to claim 3, characterized in that: The concentration of n-decanoic acid in the reaction solution is 6-15 g / L.

5. The preparation method according to claim 1, characterized in that: The temperature for the esterification reaction of the paper-based material is room temperature, and the reaction time is 4-12 hours.

6. The preparation method according to claim 1, characterized in that: The transparent paper base material is cellulose paper.

7. The preparation method according to claim 6, characterized in that: The cellulose paper comprises a cellulose component, and the structural formula of the cellulose is shown in Formula I: （Ⅰ）。 8. The preparation method according to claim 1, characterized in that: The preparation method further comprises: the paper-based material is esterified and then air-dried at room temperature to obtain the transparent hydrophobic paper.

9. The transparent hydrophobic paper prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the transparent hydrophobic paper according to claim 9 in electronic devices.

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