CN116693745A - Resin, preparation method of resin, and application of resin - Google Patents

Abstract

The application provides a resin, which comprises at least one first repeating unit and at least one second repeating unit, wherein the at least one first repeating unit is derived from a first monomer, the first monomer comprises at least one of a fluoran-based color-changing monomer and a conductive polymer-based color-changing monomer, the at least one second repeating unit is derived from a second monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of the polar functional group. The application also provides a preparation method of the resin, a resin composition containing the resin, a color-changing functional film, an electrochromic device and electronic equipment. According to the resin provided by the application, the acrylate monomer containing the polar functional group is introduced into the main chain of the resin, so that the wettability of the resin and the bonding interface can be regulated, the film forming property of the resin is improved, and the bonding strength between the resin and the bonding interface is improved.

Description

Resin, method for preparing resin, and application of resin

Technical Field

The present application relates to a resin, a method for preparing the resin, a resin composition containing the resin, a color-changing functional film prepared from the resin or the resin composition, an electrochromic device using the color-changing functional film, and an electronic device using the electrochromic device.

Background Art

Electrochromic (EC) materials are a special type of functional materials. When driven by a suitable electric field, their optical properties (color, transmittance, etc.) can change reversibly. Based on the above characteristics, electrochromic materials are widely used in energy-saving smart windows, smart anti-glare rearview mirrors, color-changing mobile phone back covers and other fields.

Traditional electrochromic materials mainly include the following: 1) Inorganic electrochromic materials represented by tungsten trioxide; 2) Small molecule electrochromic materials represented by viologens; 3) Polymer electrochromic materials represented by polythiophene; 4) Acid-base electrochromic polymer materials, etc. The above traditional electrochromic materials have weak or even no adhesion to the substrate. After applying the electrochromic materials to electronic products, there is a problem of poor reliability and poor film-forming properties, which is not conducive to large-scale coating production. In addition, most color-changing materials can only be reversibly switched between two colors, which limits the expansion of the functions of color-changing materials.

Summary of the invention

A first aspect of an embodiment of the present application provides a resin, which includes at least one first repeating unit and at least one second repeating unit, wherein the at least one first repeating unit is derived from a first monomer, wherein the first monomer includes at least one of a fluorane-type color-changing monomer and a conductive polymer-type color-changing monomer, and the at least one second repeating unit is derived from a second monomer, which is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group.

The present application forms the resin by polymerizing at least one of a fluorane-type color-changing monomer and a conductive polymer-type color-changing monomer (i.e., the first monomer) having an electrochromic function with an acrylate monomer (i.e., the second monomer) wherein the color-changing polymer formed by the selected first monomer (especially the fluorane-type color-changing monomer) has the advantages of long cycle life, rich colors, and long bistable time. An acrylate structure containing a polar functional group or its derivative is introduced into the main chain of the color-changing polymer formed by the first monomer to obtain the resin, which can make the molecular chain of the resin more flexible and the glass transition temperature (Tg) lower, thereby adjusting the wettability of the resin with the bonding interface, making the resin have better adhesion and film-forming properties, and improving the bonding strength between the resin and the bonding interface.

In some embodiments, the molar ratio of the second monomer to the first monomer is 1:(0.1-10).

In some embodiments, the polar functional group is selected from at least one of a thiol group, a hydroxyl group, an epoxy group, an amino group, and a carboxyl group.

In some embodiments, the second monomer is selected from or derived from at least one of methyl hydroxymethylacrylate, 4-tert-butylcyclohexyl acrylate, ethylene urea ethoxy methacrylate, 2-phenoxyethyl acrylate, ethyl 2-(butylamino)carbonyloxyacrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxyethoxyethyl acrylate, cyclotrimethylolpropane formal acrylate, 4-acryloylmorpholine, 2-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, ethyl 2-(ethylamino)carbonyloxyacrylate, glycidyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, and 4-hydroxybutyl acrylate.

In some embodiments, the structural formula of the resin is any one of Formula I-Formula II, and the structures of Formula I-Formula II are shown as follows:

Wherein, a and b in Formula I-Formula II are integers greater than or equal to 1;

R ₁ and R ₂ in Formula I to Formula II are independently selected from any one of H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, C ₁ -C ₂₄ alkoxy, amino, C ₁ -C ₂₄ alkylamino, C ₆ -C ₂₄ aryl, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes;

R ₄ in Formula I-Formula II is independently selected from a group containing a polar functional group or a derivative of a polar functional group;

In Formula I, R is any one of H, C ₁ -C ₂₄ alkyl, and C ₁ -C ₂₄ substituted alkyl;

_R3 in Formula I is any one of H, halogen, C1- _C24 alkyl, C1- _C24 substituted alkyl, hydroxyl, _C1 - _C24 alkoxy, amino _{, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 group containing both aromatic ring and alkane} ;

X in Formula II is any one of nitrogen, sulfur and oxygen.

In some embodiments, the resin further comprises at least one third repeating unit, wherein the at least one third repeating unit is derived from a third monomer, and the third monomer is an acrylate monomer containing a non-polar functional group or a derivative structure of a non-polar functional group.

Acrylate monomers without polar functional groups and their derivative structures are further introduced into the main chain of the resin, so as to further adjust the Tg, solubility and other properties of the resin, thereby improving the adaptability and application range of the resin.

In some embodiments, the molar ratio of the second monomer to the first monomer and the third monomer is 1:(0.1-10):(0.1-1).

In some embodiments, the third monomer is selected from at least one of butyl acrylate, amyl acrylate, benzyl acrylate, and phenylbutyl acrylate.

In some embodiments, the structural formula of the resin is any one of Formula III-Formula IV, and the structures of Formula III-Formula IV are shown as follows:

Wherein, a, b, and c in Formula III-Formula IV are integers greater than or equal to 1;

R ₁ , R ₂ , and R ₅ in Formula III to Formula IV are independently selected from any one of H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxy, C ₁ -C ₂₄ alkoxy, amino, C ₁ -C ₂₄ alkylamino, C ₆ -C ₂₄ aryl, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes;

R ₄ in Formula III to Formula IV is independently selected from a group containing a polar functional group or a derivative of a polar functional group;

In formula III, R is any one of H, C ₁ -C ₂₄ alkyl, and C ₁ -C ₂₄ substituted alkyl;

_R3 in Formula III is any one of H, halogen, C1- _C24 alkyl, C1- _C24 substituted alkyl, hydroxyl, _C1 - _C24 alkoxy, amino _{, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 group containing both aromatic ring and alkane} ;

X in Formula IV is any one of nitrogen, sulfur and oxygen.

In some embodiments, the resin also includes at least one fourth repeating unit, and the at least one fourth repeating unit is derived from a fourth monomer, and the fourth monomer includes at least one of a fluorane-type color-changing monomer, a viologen-type color-changing monomer, and a conductive polymer-type color-changing monomer, and the fourth monomer is different from the first monomer.

In some embodiments, the molar ratio of the second monomer to the first monomer and the fourth monomer is 1:(0.1-10):(0.1-10).

In some embodiments, the resin has a structural formula of any one of Formula V to Formula VII, and the structures of Formula V to Formula VII are shown below:

Wherein, a, b, and c in Formula V to Formula VII are integers greater than or equal to 1;

R ₁ -R ₂ , R ₆ -R ₈ in Formula V to Formula IV are independently selected from any one of H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxy, C ₁ -C ₂₄ alkoxy, amino, C ₁ -C ₂₄ alkylamino, C ₆ -C ₂₄ aryl, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes;

_R3 in Formula V is any one of H, halogen, C1- _C24 alkyl, C1- _C24 substituted alkyl, hydroxyl, _C1 - _C24 alkoxy, amino _{, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 group containing both aromatic ring and alkane} ;

R ₁ -R ₃ in Formula V are different from R ₆ -R ₈ ;

R ₄ in Formula V to Formula VII is independently selected from a group of polar functional groups or derivatives of polar functional groups;

In formula V and formula VII, R is any one of H, C ₁ -C ₂₄ alkyl and C ₁ -C ₂₄ substituted alkyl;

R ₅ in Formula V to Formula VII is any one of H, C ₁ -C ₂₄ alkyl and C ₁ -C ₂₄ substituted alkyl;

X in Formula VI is any one of nitrogen, sulfur and oxygen.

By further introducing other color-changing polymer monomers (fourth monomers) on the main chain of the resin (Formula I-Formula II) to form a resin (Formula V-Formula VII), the color-changing properties of the resin (Formula V-Formula VII) are further adjusted by the unique functional properties of the introduced color-changing polymer monomers, so that the molecular chain has a combination of multiple chromophores. The combination of multiple color-changing monomers also helps to achieve color regulation of the color-changing resin and the electrochromic device during the color-changing process, thereby further improving the color-changing performance of the prepared color-changing functional film and expanding the application range of the color-changing functional film.

A second aspect of an embodiment of the present application provides a resin composition, which includes the resin as described above, a fifth monomer, a second initiator, an ion transport material and an ion storage material, wherein the fifth monomer includes a polar functional group or a derivative structure thereof.

By directly mixing the ion transport material and the ion storage material with the resin, it is beneficial to uniformly disperse the ion transport material and the ion storage material in the resin and facilitate the subsequent film-forming operation; by adding the fifth monomer and the second initiator, an adhesive polymer can be formed in the subsequent film-forming process, thereby improving the bonding strength of the resin composition.

In some embodiments, the fifth monomer is an acrylate monomer containing a polar functional group or a derivative structure thereof, and the polar functional group is selected from at least one of a thiol group, a hydroxyl group, an epoxy group, an amino group, and a carboxyl group.

A third aspect of an embodiment of the present application provides another resin composition, which includes the resin as described above, a fifth monomer, a second initiator, and an ion storage material, wherein the fifth monomer includes a polar functional group or a derivative structure thereof.

By directly adding the ion transport material to the aforementioned resin, the film-forming property of the ion transport material can be improved, and the thickness of the formed film layer can be ensured to be uniform. In addition, compared with using the ion transport material alone, the color richness of the subsequently formed device is increased.

In some embodiments, the fifth monomer is an acrylate monomer containing a polar functional group or a derivative structure thereof, and the polar functional group is selected from at least one of a thiol group, a hydroxyl group, an epoxy group, an amino group, and a carboxyl group.

The fourth aspect of an embodiment of the present application provides a method for preparing a resin, which comprises mixing a first monomer and a second monomer and then adding a first initiator to polymerize and produce the resin, wherein the first monomer comprises at least one of a fluorane-type color-changing monomer and a conductive polymer-type color-changing monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group.

The resin is formed by directly polymerizing the first monomer having a color-changing function with an acrylate containing a polar functional group or its derivative under the action of an initiator. The preparation method is simple, the polymerization temperature is low, the reaction time is short, and it is conducive to industrial production.

In some embodiments, the molar ratio of the second monomer to the first monomer is 1:(0.1-10).

In some embodiments, the molar ratio of the first initiator to the sum of the contents of the first monomer and the second monomer is 1:(10-10000).

In some embodiments, the first initiator is an azo thermal initiator, a peroxide thermal initiator, or an ultraviolet light initiator.

In some embodiments, the polymerization is thermal polymerization or ultraviolet polymerization. The polymerization temperature of the thermal polymerization is 50-150° C. and the polymerization time is 0.5-8.0 h. The polymerization power of the ultraviolet polymerization is 20-200 mW/cm ² and the polymerization time is 2-20 min.

A fifth aspect of an embodiment of the present application provides a first color-changing functional film, which is formed by curing the resin composition as described above.

In some embodiments, the first color-changing functional film is used to transform from an initial color state to at least one colored state.

In some embodiments, the initial color state of the first color-changing functional film is a colorless and transparent state or a colored state.

In some embodiments, the coloring state of the first color-changing functional film is a pure color state or a superimposed color state of multiple colors.

A sixth aspect of an embodiment of the present application provides a second color-changing functional film, wherein the second color-changing functional film includes the resin as described above.

In some embodiments, the second color-changing functional film is used to transform from an initial color state to at least one colored state.

In some embodiments, the initial color state of the second color-changing functional film is a colorless and transparent state or a colored state.

In some embodiments, the coloring state of the second color-changing functional film is a pure color state or a superimposed color state of multiple colors.

A seventh aspect of an embodiment of the present application provides a third color-changing functional film, which is formed by curing another resin composition as described above.

In some embodiments, the third color-changing functional film is used to transform from an initial color state to at least one colored state.

In some embodiments, the initial color state of the third color-changing functional film is a colorless and transparent state or a colored state.

In some embodiments, the coloring state of the third color-changing functional film is a pure color state or a superimposed color state of multiple colors.

An eighth aspect of an embodiment of the present application provides a color-changing functional film, which is used to transform from an initial color state to at least two color states.

The color-changing functional film of the present application can be transformed from one initial color state to two or more coloring states. Compared with the prior art which can only transform from an initial color state to a single coloring state, the color switching mode of the color-changing functional film is increased, and the color adjustable range of the color-changing functional film is improved.

In some embodiments, the initial color state of the color-changing functional film is a colorless and transparent state or a colored state.

In some embodiments, the color-changing functional film is in a pure color state or a superimposed color state of multiple colors.

In some embodiments, the color-changing functional film includes a resin, or the color-changing functional film is cured by a resin composition, and the resin composition includes the resin, wherein the resin includes at least one first repeating unit and at least one second repeating unit, and the at least one first repeating unit is derived from a first monomer, and the first monomer includes at least one of a fluorane-type color-changing monomer and a conductive polymer-type color-changing monomer, and the at least one second repeating unit is derived from a second monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group.

A ninth aspect of an embodiment of the present application provides an electrochromic device, which includes a first electrode and a second electrode, and the first color-changing functional film as described above arranged between the first electrode and the second electrode, or the second color-changing functional film as described above, an ion transport adhesive layer and an ion storage layer stacked in sequence between the first electrode and the second electrode.

Since the first color-changing functional film and the second color-changing functional film have high bonding strength, they can have good adhesion with the first electrode and the second electrode; moreover, ion transport material and ion storage material are added to the first color-changing functional film, and the two are evenly distributed in the first color-changing functional film and are not easy to fall out, which can improve the electrochromic performance of the electrochromic device; in addition, the preparation process of the electrochromic device is simple, the film-forming property of the resin composition is good, the thickness of the resin composition film is easy to control during the coating process, and the thickness of the formed color-changing functional film is uniform. No ion transport material and ion storage material are added to the second color-changing functional film. In the process of preparing the device, the resin, ion transport material and ion storage material are respectively formed into multiple functional film layers, and each functional film layer is independently formed to reduce the interference between each functional film layer, which is conducive to improving the electrochromic effect of the electrochromic device, and each functional film layer is an independent film, which is convenient for adjusting the material components of each layer, thereby improving the application range of the electrochromic device.

In some embodiments, the ion transport adhesive layer includes an adhesive polymer containing a polar functional group or a derivative structure thereof and an ion transport material.

In some embodiments, the adhesive polymer is a polyacrylate adhesive containing a polar functional group or a derivative structure thereof.

In some embodiments, the electrochromic device also includes a transition layer located at the contact interface between the second color-changing functional membrane and the ion-transport adhesive layer, and the transition layer includes a cross-linked structure formed by cross-linking the polar functional groups in the adhesive polymer and the polar functional groups in the second color-changing functional membrane.

The second color-changing functional membrane is formed by the resin. The second color-changing functional membrane and the ion-transport bonding layer both contain polar functional groups. The polar functional groups of the two layers form a cross-linked structure at the contact interface, thereby forming a transition layer. The transition layer can improve the interface bonding force between the second color-changing functional membrane and the ion-transport bonding layer, and further provide the mechanical strength of the electrochromic device.

The tenth aspect of an embodiment of the present application provides an electrochromic device, which includes a first electrode and a second electrode, and the first color-changing functional film as described above, and/or the second color-changing functional film as described above, an ion transport adhesive layer, and the third color-changing functional film as described above, which are sequentially stacked between the first electrode and the second electrode.

By arranging the first color-changing functional film or the second color-changing functional film and the third color-changing functional film with color-changing function on the two opposite surfaces of the ion transport adhesive layer, the electrochromic device can switch between multiple colors, thereby improving the color adjustable range and structural design flexibility of the electrochromic device. The third color-changing functional film formed by mixing the ion storage material with the above-mentioned resin has a uniform thickness and a high bonding strength, so it can have good adhesion with the second electrode, thereby improving the stability and cycle life of the electrochromic device.

In some embodiments, the ion transport adhesive layer includes an adhesive polymer containing a polar functional group or a derivative structure thereof and an ion transport material.

In some embodiments, the adhesive polymer is a polyacrylate adhesive containing a polar functional group or a derivative structure thereof.

In some embodiments, the electrochromic device also includes a transition layer located at the contact interface between the ion transport adhesive layer and the second color-changing functional membrane, and/or another transition layer located at the contact interface between the ion transport adhesive layer and the third color-changing functional membrane, each of the transition layers includes a cross-linked structure formed by cross-linking the polar functional groups in the adhesive polymer with the polar functional groups in the second color-changing functional membrane or the third color-changing functional membrane.

An eleventh aspect of the embodiments of the present application provides an electrochromic device, wherein the electrochromic device is used to transform from an initial color state to at least two color states.

The electrochromic device can switch between multiple colors, and can switch from one initial color state to two or more coloring states, thereby increasing the color adjustable range of the electrochromic device.

In some embodiments, the initial color state of the electrochromic device is a colorless and transparent state or a colored state.

In some embodiments, the coloring state of the electrochromic device is a pure color state or a superimposed color state of multiple colors.

In some embodiments, the electrochromic device includes a first electrode and a second electrode, and a first color-changing functional film disposed between the first electrode and the second electrode, or a second color-changing functional film, an ion transport adhesive layer and an ion storage layer disposed between the first electrode and the second electrode. Wherein, the first color-changing functional film is cured by a resin composition, and the second color-changing functional film includes a resin, and the resin composition includes the resin, a fifth monomer, a second initiator, an ion transport material and an ion storage material, and the fifth monomer includes a polar functional group or a derivative structure thereof; the resin includes at least one first repeating unit and at least one second repeating unit, and the at least one first repeating unit is derived from the first monomer, and the first monomer includes at least one of a fluorane color-changing monomer and a conductive polymer color-changing monomer, and the at least one second repeating unit is derived from the second monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group.

In some embodiments, the resin further comprises at least one third repeating unit, wherein the at least one third repeating unit is derived from a third monomer, and the third monomer is an acrylate monomer containing a non-polar functional group or a derivative structure of a non-polar functional group.

In some embodiments, the resin also includes at least one fourth repeating unit, and the at least one fourth repeating unit is derived from a fourth monomer, and the fourth monomer includes at least one of a fluorane-type color-changing monomer, a viologen-type color-changing monomer, and a conductive polymer-type color-changing monomer, and the fourth monomer is different from the first monomer.

In some embodiments, the electrochromic device includes a first electrode and a second electrode, and a first color-changing functional film, and/or a second color-changing functional film, an ion transport adhesive layer, and a third color-changing functional film stacked sequentially between the first electrode and the second electrode. Wherein, the first color-changing functional film is cured by a resin composition, the second color-changing functional film includes a resin, and the third color-changing functional film is cured by another resin composition, the resin composition includes the resin, the fifth monomer, the second initiator, the ion transport material and the ion storage material, the fifth monomer includes a polar functional group or a derivative structure thereof, and the other resin composition includes the resin, the fifth monomer, the second initiator and the ion storage material; the resin includes at least one first repeating unit and at least one second repeating unit, the at least one first repeating unit is derived from the first monomer, the first monomer includes at least one of a fluorane color-changing monomer and a conductive polymer color-changing monomer, the at least one second repeating unit is derived from the second monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group.

A twelfth aspect of the embodiments of the present application provides an electronic device, which includes a housing and the electrochromic device as described above arranged on the housing.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of an electrochromic device provided in one embodiment of the present application.

FIG. 2 is a schematic diagram of an electrochromic device provided in another embodiment of the present application.

FIG3 is a schematic diagram of an electrochromic device provided in yet another embodiment of the present application.

FIG. 4 is a schematic diagram of an electrochromic device provided in yet another embodiment of the present application.

FIG5 is a schematic diagram of an electrochromic device provided in yet another embodiment of the present application.

FIG. 6 is a schematic diagram of an electrochromic device provided in yet another embodiment of the present application.

FIG. 7 is a schematic diagram of an electronic device provided in accordance with an embodiment of the present application.

FIG8 is a hydrogen nuclear magnetic resonance spectrum of the resin in Example 1 of the present application.

FIG. 9 is a physical picture of the resin in Example 1 of the present application formed into a film on a PET substrate.

FIG. 10 is a hydrogen nuclear magnetic resonance spectrum of the resin in Example 2 of the present application.

FIG. 11 is a physical picture of the resin in Example 2 of the present application formed into a film on a PET substrate.

FIG. 12 is a color change photograph of the single-functional layer single-color adjustable electrochromic device of the present application.

FIG. 13 is a graph showing the bistable electrochromic performance of the three-functional layer color-changing device of the present application.

FIG. 14 is a color change photograph of the single-functional-layer multi-color adjustable electrochromic device of the present application.

Main component symbols

Electrochromic devices 100,200,300,400,500,600

First electrode 1

Second electrode 2

First color-changing functional film 3a

Second color-changing functional film 3b

The third color-changing functional film 3c

Ion transport adhesive layer 4

Ion storage layer 5

Transition layer 6

Electronic equipment 700

Housing 701

DETAILED DESCRIPTION

The embodiments of the present application are described below in conjunction with the accompanying drawings in the embodiments of the present application. The data ranges involved in the present application should include the end values unless otherwise specified.

Commonly used electrochromic materials have poor film-forming properties and weak or even no adhesion to the substrate, resulting in poor reliability when the electrochromic materials are applied to electronic products.

The present application provides a resin with electrochromic function and high adhesion. The resin can be used as a color-changing functional film in an electrochromic device, but is not limited to this. The monomers for synthesizing the resin are optimized and selected so that the resin has excellent film-forming properties and adhesion properties while maintaining the electrochromic performance.

The resin includes at least one first repeating unit and at least one second repeating unit, wherein the at least one first repeating unit is derived from a first monomer, wherein the first monomer is at least one of a fluorane-type color-changing monomer and a conductive polymer-type color-changing monomer having acid-base electrochromism, and the at least one second repeating unit is derived from a second monomer, wherein the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group. That is, the resin is polymerized by a first monomer having an electrochromic function and a second monomer containing a polar functional group or a derivative of a polar functional group.

The structural formula of the resin is any one of Formula I-Formula II, and the structures of Formula I-Formula II are shown below:

Wherein, the first monomer corresponding to at least one first repeating unit in Formula I is a fluorane-based color-changing monomer, and the first monomer corresponding to at least one first repeating unit in Formula II is a conductive polymer-based color-changing monomer;

In Formula I-Formula II, a and b are both integers greater than or equal to 1;

R ₁ and R ₂ in Formula I to Formula II are independently selected from any one of H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, C ₁ -C ₂₄ alkoxy, amino, C ₁ -C ₂₄ alkylamino, C ₆ -C ₂₄ aryl, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes;

R ₄ in Formula I-Formula II is independently selected from a group containing a polar functional group or a derivative of a polar functional group;

In Formula I, R is any one of H, C ₁ -C ₂₄ alkyl, and C ₁ -C ₂₄ substituted alkyl;

_R3 in Formula I is any one of H, halogen, C1- _C24 alkyl, C1- _C24 substituted alkyl, hydroxyl, _C1 - _C24 alkoxy, amino _{, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 group containing both aromatic ring and alkane} ;

X in Formula II is any one of nitrogen, sulfur and oxygen.

For the sake of distinction, the following description of the resin in this embodiment adopts the form of resin (Formula I-Formula II).

The resin (Formula I-Formula II) provided in the present application is an electrochromic polymer, wherein the main chain of the color-changing polymer formed by the fluorane color-changing monomer and the conductive polymer color-changing monomer (especially the fluorane color-changing monomer) has a long cycle life, strong adjustability, rich colors, and can achieve switching from a fully transparent state to a colored state, and also has the advantage of a long bistable time. The main chain of the color-changing polymer formed by the above-mentioned monomer with a color-changing function is introduced into an acrylate structure containing a polar functional group, thereby obtaining the resin (Formula I-Formula II), which can make the molecular chain of the resin (Formula I-Formula II) more flexible and the glass transition temperature (Tg) lower, thereby adjusting the wettability of the resin (Formula I-Formula II) and the bonding interface, so that the resin (Formula I-Formula II) has good bonding properties and film-forming properties, and improves the bonding strength between the resin (Formula I-Formula II) and the bonding interface.

In some embodiments, _R4 includes but is not limited to at least one of thiol, hydroxyl, epoxy, amino and carboxyl groups. The second monomer includes but is not limited to methyl hydroxymethyl acrylate, 4-tert-butyl cyclohexyl acrylate, ethyl urea ethoxy methacrylate, 2-phenoxyethyl acrylate, 2-(butylamino) carbonyloxy ethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxyethoxyethyl acrylate, cyclotrimethylolpropane methylal acrylate, 4-acryloylmorpholine, 2-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, 2-(ethylamino) carbonyloxy ethyl acrylate, glycidyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-hydroxybutyl acrylate, etc.

The preparation methods of the resins (Formula I-Formula II) are respectively heating polymerization or ultraviolet (UV) polymerization according to different polymerization methods.

Heating polymerization: After the second monomer and the first monomer are mixed in a certain proportion and the first initiator is added, a linear polymer is formed by heating polymerization. The polymerization reaction temperature is 50-150°C, the polymerization reaction time is 0.5-8.0h, and the molar ratio of the second monomer to the first monomer is 1:(0.1-10). The first initiator used is a thermal initiator, which can be an azo thermal initiator or a peroxide thermal initiator. The thermal initiator includes but is not limited to diformyl peroxide, persulfate, peroxydicarbonate, and azobisisobutyronitrile. The film-forming properties and bonding properties of the resin are adjusted by the unique functional properties of these two types of functional monomers. The molar ratio of the first initiator to the mixture of the second monomer and the first monomer is 1:(10-10000).

UV polymerization: After the second monomer and the first monomer are mixed in a certain ratio and the first initiator is added, UV polymerization is used to form a linear polymer. The reaction power of UV polymerization is 20-200mW/ ^cm2 , the polymerization reaction time is 2-20min, and the molar ratio of the second monomer to the first monomer is 1:(0.1-10). The first initiator is a UV initiator, and the UV initiator includes but is not limited to 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone, 1,1'-(methylenebis-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl propiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone (benzoin dimethyl ether), 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and the like. The molar ratio of the initiator to the mixture of the second monomer and the first monomer is 1:(10-10000).

The molecular weight of the resin (Formula I-Formula II) is 1,000-120,000.

The a first repeating units and b second repeating units in the resin (Formula I-Formula II) can be arranged regularly or irregularly on the main chain of the resin, wherein a and b are positive integers greater than or equal to 1. The viscosity of the resin can be adjusted by adjusting the polymerization ratio of the first monomer and the second monomer, the amount of the first initiator, and the molecular weight of the resin (Formula I-Formula III) obtained by polymerization to meet different bonding strength requirements for the resin.

The resin (Formula I-Formula II) is used as a color-changing functional film, and its preparation method includes:

First, prepare the resin (Formula I-Formula II), and the preparation method refers to the preparation method described above;

The resin (Formula I-Formula II) is then mixed with a solvent to form a mixed glue solution, wherein the solvent can be selected from tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, etc., and the mass ratio of the resin (Formula I-Formula II) to the solvent is 1:10-1000.

The mixed adhesive solution is coated on the substrate to form an adhesive film with a certain thickness. The specific coating method can be spin coating, blade coating, spray coating or roll to roll (Roll to Roll) and the like.

The adhesive film is then heated and dried to evaporate the solvent, thereby obtaining the color-changing functional film.

By introducing an acrylate monomer containing a polar functional group into the main chain of the resin (Formula I-Formula II), the molecular chain can be made more flexible, which is beneficial to lowering the Tg of the resin (Formula I-Formula II), thereby improving the film-forming property of the resin (Formula I-Formula II) and improving the bonding strength and mechanical strength of the color-changing functional film.

It is understandable that in other embodiments, in order to make the resin (Formula I-Formula II) have other functional properties (such as adjusting the Tg, compatibility, aging resistance, etc. of the resin), on the basis of the above resin (Formula I-Formula II), at least one third repeating unit can be introduced into the main chain structure, and the at least one third repeating unit is derived from a third monomer, and the third monomer is an acrylate monomer without polar functional groups and their derivatives. The structural formula of the resin formed by polymerization is any one of Formula III-Formula IV, and the structures of Formula III-Formula IV are as follows:

Wherein, a, b, and c in Formula III-Formula IV are integers greater than or equal to 1;

R ₁ , R ₂ , and R ₅ in Formula III to Formula IV are independently selected from any one of H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxy, C ₁ -C ₂₄ alkoxy, amino, C ₁ -C ₂₄ alkylamino, C ₆ -C ₂₄ aryl, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes;

R ₄ in Formula III to Formula IV is independently selected from a group of polar functional groups or derivatives of polar functional groups;

In formula III, R is any one of H, C ₁ -C ₂₄ alkyl, and C ₁ -C ₂₄ substituted alkyl;

_R3 in Formula III is any one of H, halogen, C1- _C24 alkyl, C1- _C24 substituted alkyl, hydroxyl, _C1 - _C24 alkoxy, amino _{, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 group containing both aromatic ring and alkane} ;

X in formula IV is any one of nitrogen, sulfur and oxygen.

For the sake of distinction, the following description of the resin in this embodiment adopts the form of resin (Formula III-Formula IV).

After the second monomer is mixed with the first monomer and the third monomer in a certain proportion, a linear polymer is synthesized by heating polymerization or UV polymerization under the action of another initiator. In some embodiments, the third monomer includes but is not limited to butyl acrylate, pentyl acrylate, benzyl acrylate, butyl acrylate, etc. In some embodiments, the molar ratio of the second monomer to the first monomer and the third monomer is 1: (0.1-10): (0.1-1).

The molecular weight of the resin (Formula III-Formula IV) is 1,000-120,000.

The specific polymerization process refers to the above embodiment. The other initiator can be the above thermal initiator or UV initiator. The molar ratio of the other initiator to the mixture of the second monomer, the second type of acrylate monomer and the first monomer is 1: (10-10000).

The film-forming properties, adhesion properties, compatibility and aging resistance of the resin are adjusted by the unique functional properties of the three types of functional monomers, namely the second monomer, the first monomer and the third monomer, so as to further improve the film-forming properties, adhesion, stability and adaptability of the resin (Formula III-Formula IV), and at the same time expand the application range of the resin (Formula III-Formula IV).

The resin (Formula III-Formula IV) is used as a color-changing functional film, and its preparation method includes:

First, prepare the resin (Formula III-Formula IV), and the preparation method refers to the preparation method of the above-mentioned resin (Formula III-Formula IV);

The resin (Formula III-Formula IV) is then mixed with a solvent to form a mixed glue solution, wherein the solvent can be selected from tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, etc., and the mass ratio of the resin (Formula III-Formula IV) to the solvent is 1:10-1000.

The mixed adhesive solution is coated on the substrate to form an adhesive film with a certain thickness. The specific coating method can be spin coating, blade coating, spray coating or roll to roll (Roll to Roll) and the like.

The adhesive film is then heated and dried to evaporate the solvent, thereby obtaining the color-changing functional film.

By further introducing other functional acrylate monomers (for example, acrylate monomers containing non-polar functional groups) into the main chain of the resin (Formula I-Formula II), the film-forming properties, adhesion properties, compatibility and aging resistance of the resin (Formula III-Formula IV) are further adjusted through the unique functional properties of the functional acrylate monomers, thereby further improving the adhesion strength, mechanical strength, stability and adaptability of the prepared color-changing functional film, and at the same time expanding the application range of the color-changing functional film.

It can also be understood that in other embodiments, in order to make the resin (Formula I-Formula II) have other functional properties (such as adjusting the color switching performance of the resin), on the basis of the above-mentioned resin (Formula I-Formula II), at least one fourth repeating unit can be introduced into the main chain structure of the resin (Formula I-Formula II), and the at least one fourth repeating unit is derived from a fourth monomer, and the fourth monomer includes at least one of a fluorane color-changing monomer, a viologen color-changing monomer, and a conductive polymer color-changing monomer, and the structure of the fourth monomer should not be completely the same as the first monomer. The structural formula of the resin formed by polymerization is any one of Formula V-Formula VII, and the structures of Formula V-Formula VII are as follows:

Wherein, a, b, and c in Formula V to Formula VII are integers greater than or equal to 1;

R1-R2, R6-R8 in Formula V-Formula IV are independently selected from any one of H, halogen, C1-C24 alkyl, C1-C24 substituted alkyl, hydroxyl, C1-C24 alkoxy, amino, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 groups containing both aromatic rings and alkanes;

R3 in Formula V is any one of H, halogen, C1-C24 alkyl, C1-C24 substituted alkyl, hydroxyl, C1-C24 alkoxy, amino, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 group containing both aromatic ring and alkane;

R1-R3 and R6-R8 in Formula V are not completely the same;

R4 in Formula V to Formula VII is independently selected from a group of polar functional groups or derivatives of polar functional groups;

In formula V and formula VII, R is any one of H, C1-C24 alkyl, and C1-C24 substituted alkyl;

R5 in Formula V to Formula VII is any one of H, C1-C24 alkyl, and C1-C24 substituted alkyl;

X in Formula VI is any one of nitrogen, sulfur and oxygen.

For the sake of distinction, the following description of the resin in this embodiment adopts the form of resin (Formula V to Formula VII).

After the second monomer is mixed with the first monomer and the fourth monomer in a certain proportion, a linear polymer is synthesized by heating polymerization or UV polymerization under the action of another initiator. In some embodiments, the fourth monomer includes but is not limited to fluorane color-changing monomers, viologen color-changing monomers and conductive polymer color-changing monomers. In some embodiments, the molar ratio of the second monomer to the first monomer and the fourth monomer is 1: (0.1-10): (0.1-10).

The molecular weight of the resin (Formula III-Formula IV) is 1,000-120,000.

The specific polymerization process refers to the above-mentioned embodiment. The other initiator can be the above-mentioned thermal initiator or UV initiator. The molar ratio of the other initiator to the mixture of the second monomer, the fourth monomer and the first monomer is 1: (10-10000).

The color-changing properties of the resin are adjusted by the unique functional properties of the three types of functional monomers, namely the second monomer, the first monomer and the fourth monomer. For example, the copolymerization of different fluorane monomers can achieve new colors, and the color-changing monomers formed by copolymerization of different redox properties can obtain color-changing polymers with adjustable colors, thereby further improving the color switching performance of the resin (Formula V-Formula VII) and expanding the application range of the resin (Formula V-Formula VII).

The resin (Formula V-Formula VII) is used as a color-changing functional film, and its preparation method includes:

First, prepare the resin (Formula V-Formula VII), and the preparation method refers to the preparation method of the resin (Formula V-Formula VII) described above;

The resin (Formula V-Formula VII) is then mixed with a solvent to form a mixed glue solution, wherein the solvent can be selected from tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, etc., and the mass ratio of the resin (Formula V-Formula VII) to the solvent is 1:10-1000.

The mixed adhesive solution is coated on the substrate to form an adhesive film with a certain thickness. The specific coating method can be spin coating, blade coating, spray coating or roll to roll.

The adhesive film is then heated and dried to evaporate the solvent, thereby obtaining the color-changing functional film.

Resins (Formulas V to VII) are formed by further introducing other color-changing polymer monomers (for example, fluorane color-changing monomers, viologen color-changing monomers and conductive polymer color-changing monomers) into the main chain of the resin (Formulas I to II). The color-changing properties of the resin (Formulas V to VII) are further adjusted by the unique functional properties of the introduced color-changing polymer monomers, so that the molecular chain has a combination of multiple chromophores. The combination of multiple color-changing monomers also helps to achieve color regulation of the color-changing resin and the electrochromic device during the color-changing process, thereby further improving the color-changing performance of the prepared color-changing functional film and expanding the application range of the color-changing functional film.

The present application also provides a resin composition (I), which includes the above-mentioned resin (Formula I-Formula VII), a fifth monomer, a second initiator, an ion transport material and an ion storage material, wherein the fifth monomer includes a polar functional group or a derivative structure thereof.

The mass ratio of the resin (Formula I-Formula VII), the fifth monomer, the second initiator, the ion transport material and the ion storage material is 1: (0.5-5): (0.0001-0.05): (1-20): (0.5-5).

The fifth monomer is an acrylate monomer having a polar functional group. Specifically, the fifth monomer may be an acrylate monomer including a polar functional group or a derivative structure thereof, wherein the polar group may include but is not limited to a mercapto group, a hydroxyl group, an epoxy group, an amino group, and a carboxyl group.

The fifth monomer includes but is not limited to methyl hydroxymethylacrylate, 4-tert-butylcyclohexyl acrylate, ethylene urea ethoxy methacrylate, 2-phenoxyethyl acrylate, 2-(butylamino)carbonyloxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxyethoxyethyl acrylate, cyclotrimethylolpropane methylal acrylate, 4-acryloylmorpholine, 2-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, 2-(ethylamino)carbonyloxyethyl acrylate, glycidyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-hydroxybutyl acrylate, and the like.

The second initiator can be the aforementioned thermal initiator or UV initiator.

The ion transport material includes an electrolyte and a plasticizer, and the mass ratio of the plasticizer to the electrolyte is (1-1000): 1. The electrolyte includes but is not limited to lithium perchlorate, tetrabutylammonium hexafluorophosphate, lithium hexafluorophosphate or other ionic compounds. The plasticizer includes but is not limited to propylene carbonate, ethylene carbonate, butylene carbonate, fluoropropylene carbonate or other high boiling point solvents.

It can be understood that in other embodiments, the ion transport material can also be an ionic liquid, including but not limited to 1-butyl-4-methylpyridinium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hydrogen sulfate or other room temperature ionic liquids.

The ion storage material includes, but is not limited to, ferrocene derivatives, Prussian blue derivatives, quinone derivatives, phenol derivatives, tungsten oxide, vanadium oxide or other electrochemically active materials.

The resin composition (I) is used as the first color-changing functional film, and its preparation method includes: first preparing the resin (Formula I-Formula VII) as mentioned above, then mixing the resin (Formula I-Formula VII) with the fifth monomer, the ion transport material and the ion storage material in a certain proportion to form the resin composition (I), and then adopting a heating polymerization or UV polymerization method, under the action of a first initiator, the polar functional groups on the resin (Formula I-Formula VII) can undergo a cross-linking reaction with the polar functional groups on the fifth monomer to form a cross-linked network structure, and at the same time, the ion transport material and the ion storage material are uniformly dispersed in the network structure. Wherein, the polymerization reaction temperature of the thermal polymerization is 50-150°C, and the polymerization reaction time is 0.5-8.0h; the polymerization reaction power of the UV polymerization is 20-200mW/ ^cm2 , and the polymerization reaction time is 2-20min.

The obtained first color-changing functional film can be used to transform from an initial state to at least one coloring state, specifically, it can realize the switching from one coloring state to another coloring state (for example, it can be switched from red to blue), and it can also realize the switching from one coloring state to other multiple coloring states (for example, it can be switched from red to blue, or green, or other colors). Among them, the initial coloring state of the first color-changing functional film can be a colorless and transparent state, or a colored coloring state; the colored state of the first color-changing functional film can be a pure coloring state, or a superimposed coloring state of multiple colors.

The cross-linked network structure is formed by the acrylate adhesive monomer with polar functional groups and the above-mentioned resin (Formula I-Formula VII) with polar functional groups, which is beneficial to the compatibility of the resin (Formula I-Formula VII) with the fifth monomer, and the cross-linked network structure formed improves the bonding strength and mechanical strength of the first color-changing functional film; moreover, the ion transport material and the ion storage material can be evenly dispersed in the network structure, and under the constraint of the network structure, the risk of ion transport material and ion storage material coming out is reduced, and the performance stability of the first color-changing functional film is improved. In addition, the first color-changing functional film obtained has ion transport, ion storage and color-changing functions at the same time, which increases the flexibility of the subsequent device structure and the diversity of device color adjustment.

The present application also provides another resin composition (II), which includes the above-mentioned resin (Formula I-Formula VII), a fifth monomer, a second initiator, and an ion storage material. The fifth monomer, the second initiator, and the ion storage material can refer to the aforementioned materials, and no further details are given here.

Wherein, the mass ratio of the resin (Formula I-Formula VII), the fifth monomer, the second initiator and the ion storage material is 1:(0.5-5):(0.0001-0.05):(0.5-5).

The resin composition (II) is used as the third color-changing functional film, and its preparation method refers to the method for preparing the second color-changing functional film using the above-mentioned resin composition (I).

The obtained third color-changing functional film can be used to transform from an initial state to at least one coloring state, specifically, it can realize the switching from one coloring state to another coloring state (for example, it can be switched from red to blue), and it can also realize the switching from one coloring state to other multiple coloring states (for example, it can be switched from red to blue, or green, or other colors). Wherein, the initial coloring state of the third color-changing functional film can be a colorless and transparent state, or a colored coloring state; the colored state of the third color-changing functional film can be a pure coloring state, or a superimposed coloring state of multiple colors.

The cross-linked network structure is formed by the acrylate adhesive monomer with polar functional groups and the above-mentioned resin with polar functional groups (Formula I-Formula VII), which is beneficial to the compatibility of the resin (Formula I-Formula VII) with the fifth monomer, and the formed cross-linked network structure improves the bonding strength and mechanical strength of the third color-changing functional membrane; and the ion storage material can be evenly dispersed in the network structure. Under the constraint of the network structure, the risk of ion storage material escaping is reduced, and the performance stability of the third color-changing functional membrane is improved; in addition, combining the ion storage material with the resin (Formula I-Formula VII) to form the third color-changing functional membrane can enable the third color-changing functional membrane to have both ion storage function and color-changing function, thereby increasing the flexibility of the subsequent device structure and the diversity of device color adjustment.

An embodiment of the present application provides a color-changing functional film, which is used to transform from an initial color state to at least two coloring states. That is, the color-changing functional film can achieve switching from one color state to two or more other color states (for example, it can switch from red to blue, or green, or other colors). Among them, the initial color state of the color-changing functional film can be a colorless and transparent state, or a colored color state; the coloring state of the color-changing functional film can be a pure color state, or a superimposed color state of multiple colors. Compared with the prior art that can only transform from an initial color state to a single coloring state, the color-changing functional film provided in this embodiment can achieve transformation from an initial color state to multiple coloring states, thereby improving the color controllable range of the color-changing functional film and expanding the application range of the color-changing functional film.

In this embodiment, the color-changing functional film can be prepared by using the aforementioned resin or resin composition (I, or II). For the specific preparation method, please refer to the preparation method of the aforementioned color-changing functional film.

As shown in FIG1 , an embodiment of the present application provides an electrochromic device 100, the electrochromic device 100 comprising a first color-changing functional film 3a, a first electrode 1 and a second electrode 2, wherein the first electrode 1 and the second electrode 2 are located on opposite surfaces of the first color-changing functional film 3a. The first color-changing functional film 3a is a color-changing functional film prepared using the resin composition (I) as described above. Since there is only one layer of color-changing functional film 3a between the first electrode 1 and the second electrode 2, the electrochromic device 100 is also referred to as a single-functional layer electrochromic device.

The first electrode 1 and the second electrode 2 both include a substrate (e.g., a glass plate, a plastic plate, etc., not shown) and a conductive layer (not shown) located on the surface of the substrate, and the conductive layer may be made of metal, doped metal oxide such as indium tin oxide (ITO), or fluorine-doped tin dioxide (FTO), etc. The first color-changing functional film 3a is located on the surface of the conductive layer away from the substrate.

The thickness of the first color-changing functional film 3a is 5-500 μm.

The preparation method of the electrochromic device 100 is:

First, the resin composition (I) is coated on the surface of the conductive layer of the first electrode 1 to form a resin composition film. Specifically, the coating method may be spin coating, blade coating, spray coating or roll to roll coating.

The second electrode 2 is then attached to the surface of the resin composition (I) film, and thermal polymerization or UV polymerization curing is performed (the specific method is described above), thereby obtaining the electrochromic device 100.

The obtained electrochromic device 100 can be used to transform from an initial state to at least one coloring state, specifically, it can realize the switching from one coloring state to another coloring state (for example, it can be switched from red to blue), and it can also realize the switching from one coloring state to other multiple coloring states (for example, it can be switched from red to blue, or green, or other colors). Among them, the initial coloring state of the electrochromic device 100 can be a colorless and transparent state, or a colored coloring state; the colored state of the electrochromic device 100 can be a pure coloring state, or a superimposed coloring state of multiple colors.

Since the first color-changing functional film 3a has a high bonding strength, it can have good adhesion with the first electrode 1 and the second electrode 2; and, due to the cross-linked network structure of the first color-changing functional film 3a, the ion transport material and the ion storage material can be evenly distributed and not easy to fall out, which can improve the electrochromic performance of the electrochromic device 100; in addition, the preparation process of the electrochromic device 100 is simple, the film-forming property of the resin composition is good, the thickness of the resin composition film is easy to control during the coating process, and the thickness of the first color-changing functional film 3a formed is uniform. At the same time, the electrochromic device 100 has excellent electrochromic properties such as long cycle life, rich colors, and long bistable time.

As shown in FIG2 , another embodiment of the present application provides an electrochromic device 200, which includes a first electrode 1, a second color-changing functional film 3b, a transition layer 6, an ion transport adhesive layer 4, an ion storage layer 5, and a second electrode 2 stacked in sequence. Since the second color-changing functional film 3b, the ion transport adhesive layer 4, and the ion storage layer 5 are provided between the first electrode 1 and the second electrode 2, the electrochromic device 200 is also referred to as a three-layer functional electrochromic device.

The second color-changing functional film 3b is a color-changing functional film prepared by using the resin (Formula I to Formula VII) as described above.

The thickness of the second color-changing functional film 3b is 5-500nm, preferably 20-200nm; the thickness of the ion transport adhesive layer 4 is 5-500μm, preferably 10-50μm; the thickness of the ion storage layer 5 is 5-500nm, preferably 20-200nm.

The ion transport adhesive layer 4 is made by curing the ion transport adhesive composition, which includes a fifth monomer, a second initiator, and an ion transport material, and the mass ratio of the fifth monomer, the second initiator, and the ion transport material is 1: (0.0001-0.01): (0.2-20). The fifth monomer is the aforementioned fifth monomer.

Since the fifth monomer is an acrylate monomer having polar functional groups such as mercapto, hydroxyl, epoxy, amino, carboxyl, etc., or a derivative structure of the above monomers, after the fifth monomer is polymerized under the action of the second initiator to form an adhesive polymer, the main chain of the adhesive polymer contains polar functional groups. Therefore, during the molding process of the electrochromic device, the polar functional groups on the main chain of the adhesive polymer and the polar functional groups on the main chain of the resin (Formula I-Formula VII) forming the second color-changing functional film 3b can be cross-linked to form a cross-linked structure. Therefore, the contact interface between the second color-changing functional film 3b and the ion transport adhesive layer 4 will form the transition layer 6. Due to the cross-linked structure in the transition layer 6, the interfacial bonding force between the second color-changing functional film 3b and the ion transport adhesive layer 4 is improved, and the overall performance of the overall electrochromic device 200 is further improved.

The second initiator can be the aforementioned thermal initiator or UV initiator.

The specific components of the ion transport material are as mentioned above.

The ion storage layer 5 includes an ion storage material, a film-forming agent and a solvent, wherein the mass ratio of the ion storage material, the film-forming agent and the solvent is 1: (10-100): (20-500). The specific components of the ion storage material are as mentioned above. The film-forming agent includes but is not limited to acrylate polymers, acrylonitrile polymers, etc. The solvent includes but is not limited to tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, etc.

The preparation method of the electrochromic device 200 is:

First, the resin (Formula I to Formula VII) is coated on the surface of the conductive layer of the first electrode 1 to form a resin film. Specifically, the coating method may be spin coating, blade coating, spray coating or roll to roll coating.

A layer of ion transport adhesive composition is coated on the surface of the resin film. Specifically, a coating method such as spin coating, blade coating, spray coating or roll to roll coating can be adopted.

Then, the ion storage composition is coated on the surface of the conductive layer of the second electrode 2 . Specifically, the coating method may be spin coating, scraper coating, spray coating or roll to roll coating.

Finally, the second electrode 2 coated with the ion storage composition is attached to the surface of the ion transport adhesive composition, and thermal polymerization or UV polymerization curing is performed (the specific method is described above), thereby obtaining the electrochromic device 200.

The obtained electrochromic device 200 can be used to transform from an initial state to at least one coloring state, specifically, it can realize the switching from one coloring state to another coloring state (for example, it can be switched from red to blue), and it can also realize the switching from one coloring state to other multiple coloring states (for example, it can be switched from red to blue, or green, or other colors). Among them, the initial coloring state of the electrochromic device 200 can be a colorless and transparent state, or a colored coloring state; the colored state of the electrochromic device 200 can be a pure coloring state, or a superimposed coloring state of multiple colors.

Since the second color-changing functional film 3b of the present application has a high bonding strength, it can have good adhesion with the first electrode 1. In addition, the resin (Formula I-Formula VII) has good film-forming properties, the thickness of the resin film is easy to control during the coating process, and the thickness of the formed second color-changing functional film 3b is uniform.

The resin film is formed by the resin (Formula I-Formula VII), the molecular main chain of the resin (Formula I-Formula VII) includes an acrylate monomer containing a polar functional group, and the acrylate monomer containing a polar functional group exists in the ion transfer adhesive composition, which improves the compatibility of the resin (Formula I-Formula VII) and the fifth monomer at the contact interface. During the polymerization and curing process, the fifth monomer is polymerized to form an adhesive polymer under the action of the second initiator, and the polar functional groups on the main chain of the adhesive polymer are cross-linked with the polar functional groups on the main chain of the resin (Formula I-Formula VII) to form a transition layer 6 with a cross-linked structure, thereby improving the bonding strength between the second color-changing functional film 3b and the ion transfer adhesive layer 4, so that the electrochromic device 200 has excellent electrochromic properties such as long cycle life, rich colors, and long bistable time, while also improving the mechanical strength of the electrochromic device 200 and the stability of the electrochromic performance.

As shown in Figure 3, another embodiment of the present application provides an electrochromic device 300, which includes a first electrode 1, the second color-changing functional film 3b as described above, a transition layer 6, an ion transport adhesive layer 4, a transition layer 6, the third color-changing functional film 3c as described above, and a second electrode 2 stacked in sequence.

The difference between the preparation method of the electrochromic device 300 and the preparation method of the electrochromic device 200 of the aforementioned embodiment is that the resin composition (II) as described above is coated on the surface of the conductive layer of the second electrode 2 to form a resin film, and the specific coating method can be a coating method such as spin coating, scraper coating, spray coating or roll to roll coating. For other preparation methods, please refer to the above, and no further details will be given here.

The obtained electrochromic device 300 can be used to transform from an initial state to at least one coloring state, specifically, it can realize the switching from one coloring state to another coloring state (for example, it can be switched from red to blue), and it can also realize the switching from one coloring state to other multiple coloring states (for example, it can be switched from red to blue, or green, or other colors). Due to the addition of the third color-changing functional film 3c, it is particularly advantageous to realize the latter. Among them, the initial coloring state of the electrochromic device 300 can be a colorless and transparent state, or a colored coloring state; the colored state of the electrochromic device 300 can be a pure coloring state, or a superimposed coloring state of multiple colors.

By forming a film layer with a color-changing function on the two opposite surfaces of the ion transport adhesive layer 4, the color adjustment range of the electrochromic device 300 can be increased, and the flexibility and color richness of the device color adjustment can be improved. The film-forming property of the resin (Formula I-Formula VII) is good, and the thickness of the resin film is easy to control during the coating process. The thickness of the third color-changing functional film 3c formed by mixing the ion storage material with the aforementioned resin (Formula I-Formula VII) is uniform and has a high bonding strength. Therefore, it can have good adhesion with the second electrode 2, and a transition layer 6 with a cross-linked structure is formed between the ion transport adhesive layer 5, thereby improving the stability and cycle life of the electrochromic device 300.

As shown in Figure 4, another embodiment of the present application provides an electrochromic device 400, which includes a first electrode 1, the first color-changing functional film 3a as described above, a transition layer 6, an ion transport adhesive layer 4, a transition layer 6, the third color-changing functional film 3c as described above, and a second electrode 2 stacked in sequence.

The difference between the preparation method of the electrochromic device 400 and the preparation method of the electrochromic device 200 of the aforementioned embodiment is that: the resin composition (I) as described above is coated on the surface of the conductive layer of the first electrode 1 to form a resin film, and the resin composition (II) as described above is coated on the surface of the conductive layer of the second electrode 2 to form a resin film. The specific coating method can be a coating method such as spin coating, scraper coating, spray coating or roll to roll coating. For other preparation methods, please refer to the above, and no further details are given here.

The obtained electrochromic device 400 can be used to transform from an initial state to at least one coloring state, specifically, it can realize the switching from one coloring state to another coloring state (for example, it can be switched from red to blue), and it can also realize the switching from one coloring state to other multiple coloring states (for example, it can be switched from red to blue, or green, or other colors). Due to the addition of the third color-changing functional film 3c, it is particularly advantageous to realize the latter. Among them, the initial coloring state of the electrochromic device 400 can be a colorless and transparent state, or a colored coloring state; the colored state of the electrochromic device 400 can be a pure coloring state, or a superimposed coloring state of multiple colors.

As shown in FIG5 , another embodiment of the present application provides an electrochromic device 500, the electrochromic device 500 includes a first electrode 1, a second electrode 2, and the first color-changing functional film 3a as described above, the second color-changing functional film 3b as described above, a transition layer 6, an ion transport adhesive layer 4, a transition layer 6, and the third color-changing functional film 3c as described above, which is stacked between the first electrode 1 and the second electrode 2. The ion transport adhesive layer 4 is located between the second color-changing functional film 3b and the third color-changing functional film 3c. The specific position of the first color-changing functional film 3a is not limited. In this embodiment, the first color-changing functional film 3a can be located on the side of the second color-changing functional film 3b away from the ion transport adhesive layer 4.

The difference between the preparation method of the electrochromic device 500 and the preparation method of the electrochromic device 200 of the aforementioned embodiment is that: the resin composition (I) as described above is applied on the surface of the conductive layer of the first electrode 1 to form a resin film, and the resin (Formula I-Formula VII) as described above is applied on the surface of the formed resin film to form another resin film, and then the ion transport adhesive composition is applied on the other resin film; in addition, the resin composition (II) as described above is applied on the surface of the conductive layer of the second electrode 2 to form another resin film. The specific coating method can be a coating method such as spin coating, scraping, spraying or roll to roll (Roll to Roll). For other preparation methods, please refer to the above, and no further details will be given here.

The obtained electrochromic device 500 can be used to transform from an initial state to at least one coloring state, specifically, it can realize the switching from one coloring state to another coloring state (for example, it can be switched from red to blue), and it can also realize the switching from one coloring state to other multiple coloring states (for example, it can be switched from red to blue, or green, or other colors). Due to the addition of the third color-changing functional film 3c, it is particularly advantageous to realize the latter. Among them, the initial coloring state of the electrochromic device 500 can be a colorless and transparent state, or a colored coloring state; the colored state of the electrochromic device 500 can be a pure coloring state, or a superimposed coloring state of multiple colors.

As shown in FIG6 , another embodiment of the present application provides an electrochromic device 600, which is used to transform from an initial color state to at least two coloring states. That is, the electrochromic device 600 can realize the switching from one color state to two or more other color states (for example, it can be switched from red to blue, or green, or other colors). Among them, the initial color state of the electrochromic device 600 can be a colorless transparent state, or a colored color state; the coloring state of the electrochromic device 600 can be a pure color state, or a superimposed color state of multiple colors. Compared with the prior art that can only transform from an initial color state to a single coloring state, the electrochromic device 600 provided in this embodiment can realize the transformation from an initial color state to multiple coloring states, thereby improving the color controllable range of the electrochromic device 600.

In this embodiment, the electrochromic device 600 can be prepared by using the aforementioned color-changing functional film. For the specific preparation method, please refer to the preparation method of the aforementioned electrochromic device.

As shown in FIG7 , an embodiment of the present application provides an electronic device 700 using the above-mentioned electrochromic device 100 (200, 300, 400, 500, 600), and the electronic device 700 includes a housing 701 and the above-mentioned electrochromic device 100 (200, 300, 400, 500, 600) mounted on the housing 701. The electronic device 700 can be an energy-saving smart window, a smart anti-glare rearview mirror, a color-changing mobile phone back cover, etc., but is not limited thereto. In this embodiment, the electronic device 700 is a smart anti-glare rearview mirror.

The embodiments of the present application are further described below through specific examples.

Embodiment 1

(1) Preparation of a color-changing resin (UV polymerization) with adhesion properties:

First, the first monomer (in this example, the first monomer can be reversibly switched between colorless and blue and belongs to the fluorane monomer) and the second monomer (in this example, tetrahydrofuran acrylate is selected) are mixed in a molar ratio of 1: (0.1~1), and the first initiator (in this example, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone is selected as the initiator) is added, and the molar ratio of the first initiator to the sum of the two monomers is 1: (100~10000)), and the mixture is stirred and dissolved to obtain a reaction solution.

The reaction solution is then irradiated with an LED lamp to initiate polymerization to obtain a product, and the obtained product is placed in a vacuum oven for drying to obtain the resin.

The structural formula VIII of the obtained resin is shown below:

(2) Preparation of a color-changing functional film with adhesion properties:

The product after drying in (1) is dissolved in a solvent (tetrahydrofuran is selected in this example), spin-coated on a substrate (PET substrate is selected in this example) to form a film, and the solvent is dried again to obtain the color-changing functional film.

Technical Effects of Embodiment 1

As shown in FIG8 , the hydrogen nuclear magnetic resonance spectrum of the color-changing resin with adhesion properties is given. From the hydrogen spectrum ¹ H-NMR (ppm, CDCl ₃ -d6) in FIG8 , it can be seen that δ=1.58 (1H, H ⁵ ), δ=1.86 (3H, H ¹ , H ² , H ³ ), δ=3.00 (1H, H ⁹ ), δ=6.38-7.17 (8H, 13-20 hydrogen), δ=8.11 (1H, H ¹² ). From the hydrogen spectrum, it can be judged that the resin with adhesion and color-changing functions has been successfully synthesized.

As shown in Figure 9, it is a photograph of the color-changing functional film obtained by forming the above-mentioned resin into a film on a PET substrate and drying it. It can be seen from Figure 9 that the resin has good film-forming properties and can form a color-changing functional film of uniform thickness. The appearance of the color-changing functional film has no wrinkles or unevenness.

The color-changing functional film with adhesion properties obtained in this embodiment has excellent adhesion to the substrate.

Embodiment 2

(1) Preparation of a color-changing resin (thermal polymerization) with adhesion properties:

First, the first monomer (in this case, the first monomer can be reversibly switched between colorless and blue, and belongs to the fluorane monomer) is mixed with the second monomer (in this case, ethoxyethoxyethyl acrylate is selected), and the molar ratio of the two is 1: (0.1-1), and the first initiator (in this case, azobisisobutyronitrile is selected as the initiator), the molar ratio of the first initiator to the sum of the two monomers is 1: (100-10000), and the mixture is stirred and dissolved to obtain a reaction solution. The system is vacuumed and filled with nitrogen to remove oxygen in the system. After that, it is heated and polymerized to obtain an intermediate product. The intermediate product is dissolved in an appropriate amount of tetrahydrofuran, and the dissolved intermediate product is dripped into an excess of anhydrous ethanol to obtain a large amount of white precipitate. The above white precipitate is then filtered and dried to obtain the resin.

The structural formula IX of the obtained resin is shown below:

(2) Preparation of a color-changing functional film with adhesion properties:

The resin dried in (1) is dissolved in a solvent (tetrahydrofuran is selected in this example), spin-coated on a substrate (PET substrate is selected in this example) to form a film, and dried again to remove the solvent, thereby obtaining the color-changing functional film.

Technical Effects of Embodiment 2

As shown in FIG10 , the nuclear magnetic resonance hydrogen spectrum of the color-changing resin with adhesion properties is given. From the nuclear magnetic resonance hydrogen spectrum ¹ H-NMR (ppm, CDCl ₃ -d6) in FIG10 , it can be seen that δ=1.33 (6H, 1 to 6 hydrogens), δ=1.56 (1H, H ⁷ ), δ=3.05 (1H, H ¹¹ ), δ=6.42 to 7.21 (8H, 15 to 22 hydrogens), δ=8.18 (1H, H ¹⁴ ). From the hydrogen spectrum, it can be judged that the resin with adhesion and color-changing functions has been successfully synthesized.

As shown in Figure 11, it is a photograph of the color-changing functional film obtained by forming the above-mentioned resin into a film on a PET substrate and drying it. It can be seen from Figure 11 that the resin has good film-forming properties and can form a color-changing functional film of uniform thickness. The appearance of the color-changing functional film has no wrinkles or unevenness.

The color-changing functional film with adhesion properties obtained in this embodiment has excellent adhesion to the substrate.

Embodiment 3

Preparation of single functional layer electrochromic devices:

First, the color-changing resin with adhesion properties prepared in Example 1, the fifth monomer containing a polar functional group (4-acryloylmorpholine is selected in this example), the second initiator (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone is selected in this example), the ion storage material (benzoquinone is selected in this example), and the ion transport material (a mixture of a plasticizer and an electrolyte, specifically a mixture of ethylene carbonate and lithium perchlorate, with a mass ratio of 1:(0.1-1)) are mixed in a mass ratio of 1:(2-20):(0.001-0.1):(0.2-2):(1-10), and stirred to obtain a resin composition.

Then, the resin composition is coated on the surface of the first electrode (in this case, PET loaded with ITO, referred to as PET-ITO electrode, with a square resistance of 20 to 50 Ω/sq) to form a thin film, and then covered with the second electrode (also PET-ITO electrode), and the thin film of the resin composition is irradiated and cured with a UV lamp, and a single-functional layer electrochromic device is obtained after curing.

Table 1

Peel force(N) Coloring time(s) Fading time(s) Contrast(%) Device 1 5.4 10 15 52 Device 2 5 10 12 54 Device 3 5.5 10 11 55

As shown in FIG12 , the single-functional layer electrochromic device prepared in this embodiment can switch between colorless and blue under the control of voltage. Table 1 shows the corresponding performance of the single-functional layer electrochromic device. In this embodiment, multiple devices (devices 1-3 in Table 1) are prepared in the same way to test their peeling force and electrochromic performance (such as color change and fading time and its corresponding contrast change). It can be seen that devices 1-3 have good repeatability, can achieve a transmittance change of more than 50% in a short time, and have a peeling force greater than or equal to 5N, which can better meet the requirements of the electrochromic device for bonding strength. It can be seen that the single-functional layer electrochromic device prepared based on this color-changing resin has excellent electrochromic performance such as long cycle life, rich colors, and long bistable time, and the electrochromic functional layer also has a large bonding force.

Embodiment 4

Preparation of three-layer functional electrochromic devices:

First, the color-changing resin with adhesion properties prepared in Example 1 is dissolved in a solvent (tetrahydrofuran in this example) to obtain a polymer solution, and the polymer solution is spin-coated on the surface of the first electrode (PET-ITO electrode in this example), and heated to evaporate the solvent to form a film, thereby obtaining a color-changing functional film.

The ion storage material (in this case, inorganic material _TiO2 nanoparticles), film-forming agent (in this case, acrylic polymer), and solvent (in this case, tetrahydrofuran) are mixed and spin-coated on the surface of the second electrode (PET-ITO electrode) to form a film and then dried to obtain an ion storage layer.

An ion transport adhesive composition is obtained by mixing a fifth monomer containing a polar functional group (in this case, 4-acryloylmorpholine), a second initiator (in this case, the initiator 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone) and an ion transport material (in this case, a mixture of a plasticizer and an electrolyte, specifically a mixture of ethylene carbonate and lithium perchlorate, with a mass ratio of 1:(0.1-1)) in a mass ratio of (2-10):(0.001-0.1):(0.2-1).

The obtained ion transport adhesive composition is applied on the surface of the obtained color-changing functional film to form a film.

The second electrode coated with the ion storage layer is covered on the surface of the ion transport adhesive composition, and is irradiated and cured by a UV lamp, and a three-layer functional electrochromic device is obtained after curing.

As shown in FIG13 , the three-functional layer monochromatic adjustable electrochromic device prepared in this embodiment has a certain bistable property. When a suitable voltage is applied, the device can switch from colorless to blue. After the voltage is removed, the blue color of the device can be maintained. When a suitable opposite voltage is applied, the color of the device fades. Therefore, the three-functional layer electrochromic device has excellent electrochromic properties such as long cycle life, rich colors, and long bistable time. In addition, this electrochromic functional layer has good adhesion performance.

Embodiment 5

(1) Preparation of novel color-changing resin containing multiple chromophores:

A first monomer (a fluorane color-changing resin monomer having the ability to switch from colorless to blue), a fourth monomer (a fluorane color-changing resin monomer having the ability to switch from colorless to red) and a second monomer (tetrahydrofuran acrylate is selected in this example) are mixed, wherein the molar ratio of the second monomer to the first monomer and the fourth monomer is 1:(0.1-10):(0.1-10), and copolymerization is carried out according to the above-mentioned polymerization method to obtain a novel multi-chromophore color-changing resin.

(2) Preparation of single-functional-layer multicolor tunable electrochromic devices:

The multi-chromophore color-changing resin prepared in (1) was prepared according to the method of Example 3 to obtain a single-functional layer multi-color adjustable electrochromic device.

As shown in Figure 14, the single-functional layer multi-color adjustable electrochromic device prepared in this embodiment can switch between colorless, red and blue under the control of different voltages. It can be seen that by introducing multiple chromophores into the main chain of the resin molecule, a combination based on multiple chromophores can be achieved. The single-functional layer electrochromic device prepared by this color-changing resin can switch between multiple colors, thereby increasing the color adjustable range of the color-changing resin and expanding the application range of the color-changing resin.

It should be noted that the above are only specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application, which should be included in the protection scope of the present application; in the absence of conflict, the implementation methods of the present application and the features in the implementation methods can be combined with each other. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims (53)

1. A resin characterized in that it comprises at least one first repeating unit and at least one second repeating unit, the at least one first repeating unit is derived from a first monomer comprising fluoranes At least one of a color-changing monomer and a conductive polymer-based color-changing monomer, the at least one second repeating unit is derived from a second monomer, and the second monomer is a derivative structure containing a polar functional group or a polar functional group acrylate monomers. 2. The resin according to claim 1, characterized in that, the molar ratio of the second monomer to the first monomer is 1:(0.1-10). 3. The resin according to claim 1, wherein the polar functional group is selected from at least one of mercapto, hydroxyl, epoxy, amino and carboxyl. 4. The resin according to claim 2, wherein the second monomer is selected from or derived from methylol methacrylate, 4-tert-butylcyclohexyl acrylate, ethylene urea methacrylate 2-phenoxyethyl acrylate, 2-(butylamino)carbonyloxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxyethoxyethyl acrylate ester, cyclotrimethylolpropane formal acrylate, 4-acryloylmorpholine, 2-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, 2-(ethyl At least one of ethyl amino) carbonyl oxyacrylate, glycidyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, and 4-hydroxybutyl acrylate. 5. according to the resin described in any one in claim 1 to 4, it is characterized in that, the structural formula of described resin is any one in formula I-formula II, and the structure of formula I-formula II is as follows: Wherein, a and b in Formula I-Formula II are all integers greater than or equal to 1; R ₁ and R ₂ in Formula I-Formula II are independently selected from H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, C ₁ -C ₂₄ Any one of alkoxy, amino, C ₁ -C ₂₄ alkylamino, C ₆ -C ₂₄ aryl, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes; R in formula I-II are _{independently} selected from groups containing polar functional groups or derivatives of polar functional groups; R in formula I is any one of H, C ₁ -C ₂₄ alkyl and C ₁ -C ₂₄ substituted alkyl; R ₃ in formula I is H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, C ₁ -C ₂₄ alkoxy, amino, C ₁ - Any one of C ₂₄ alkylamino group, C ₆ -C ₂₄ aryl group, and C ₇ -C ₂₄ group containing both aromatic ring and alkane; X in formula II is any one of nitrogen, sulfur and oxygen. 6. The resin according to claim 1, further comprising at least one third repeating unit derived from a third monomer containing Acrylate monomers with non-polar functional groups or derivative structures of non-polar functional groups. 7. The resin according to claim 6, wherein the molar ratio of the second monomer to the first monomer and the third monomer is 1: (0.1-10): (0.1- 1). 8 . The resin according to claim 6 , wherein the third monomer is selected from at least one of butyl acrylate, pentyl acrylate, benzyl acrylate and phenyl butyl acrylate. 9. resin according to claim 6, is characterized in that, the structural formula of described resin is any one in formula III-formula IV, and the structure of formula III-formula IV is as follows: Wherein, a, b, and c in formula III-formula IV are all integers greater than or equal to 1; R ₁ , R ₂ , and R ₅ in Formula III-Formula IV are independently selected from H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, C ₁ - Any one of C ₂₄ alkoxy, amino, C ₁ -C ₂₄ alkylamino, C ₆ -C ₂₄ aryl, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes kind; R in formula III-formula _IV are independently selected from groups containing polar functional groups or derivatives of polar functional groups; R in formula III is any one of H, an alkyl group between C ₁ -C ₂₄ and a substituted alkyl group between C ₁ -C ₂₄ ; R ₃ in formula III is H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, C ₁ -C ₂₄ alkoxy, amino, C ₁ - Any one of C ₂₄ alkylamino group, C ₆ -C ₂₄ aryl group, and C ₇ -C ₂₄ group containing both aromatic ring and alkane; X in formula IV is any one of nitrogen, sulfur and oxygen. 10. The resin according to claim 1, further comprising at least one fourth repeating unit derived from a fourth monomer comprising a fluorescent At least one of alkane-based color-changing monomers, viologen-based color-changing monomers, and conductive polymer-based color-changing monomers, the fourth monomer is different from the first monomer. 11. The resin according to claim 10, wherein the molar ratio of the second monomer to the first monomer and the fourth monomer is 1: (0.1-10): (0.1- 10). 12. resin according to claim 10, is characterized in that, the structural formula of described resin is any one in formula V-formula VII, and the structure of formula V-formula VII is as follows: Wherein, a, b, and c in formula V-formula VII are all integers greater than or equal to 1; R ₁ -R ₂ in Formula V-Formula IV, R ₆ -R ₈ are independently selected from H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, Among C ₁ -C ₂₄ alkoxy groups, amino groups, C ₁ -C ₂₄ alkylamino groups, C ₆ -C ₂₄ aryl groups, and C ₇ -C ₂₄ groups containing both aromatic rings and alkanes any of R ₃ in formula V is H, halogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ substituted alkyl, hydroxyl, C ₁ -C ₂₄ alkoxy, amino, C ₁ - Any one of C ₂₄ alkylamino group, C ₆ -C ₂₄ aryl group, and C ₇ -C ₂₄ group containing both aromatic ring and alkane; R ₁ -R ₃ in formula V are different from R ₆ -R ₈ ; _R in formula V-formula VII are independently selected from polar functional groups or groups of derivatives of polar functional groups; R in formula V and formula VII is any one of H, C ₁ -C ₂₄ alkyl and C ₁ -C ₂₄ substituted alkyl; R ₅ in Formula V-Formula VII is any one of H, an alkyl group between C ₁ -C ₂₄ and a substituted alkyl group between C ₁ -C ₂₄ ; X in formula VI is any one of nitrogen, sulfur and oxygen. 13. A resin composition, characterized in that, comprising the resin according to any one of claims 1 to 12, a fifth monomer, a second initiator, an ion transport material and an ion storage material, the fifth Monomers include polar functional groups or derivative structures thereof. 14. The resin composition according to claim 13, wherein the fifth monomer is an acrylate monomer containing a polar functional group or a derivative structure thereof, and the polar functional group is selected from the group consisting of mercapto, hydroxyl, ring At least one of oxy, amino and carboxyl. 15. A resin composition, characterized in that, comprising the resin according to any one of claims 1 to 12, a fifth monomer, a second initiator and an ion storage material, the fifth monomer comprising a polar Sexual functional groups or their derivative structures. 16. The resin composition according to claim 15, wherein the fifth monomer is an acrylate monomer containing a polar functional group or a derivative structure thereof, and the polar functional group is selected from the group consisting of mercapto, hydroxyl, ring At least one of oxy, amino and carboxyl. 17. A method for preparing a resin, characterized in that, after mixing the first monomer and the second monomer, adding the first initiator to polymerize the resin, the first monomer includes fluoran-based color-changing monomers and At least one of the conductive polymer-based color-changing monomers, the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of the polar functional group. 18. The preparation method of the resin according to claim 17, characterized in that, the molar ratio of the second monomer to the first monomer is 1:(0.1-10). 19. the preparation method of resin according to claim 17 is characterized in that, the mol ratio of the content sum of described first initiator and described first monomer and described second monomer is 1:(10 -10000). 20. The preparation method of the resin according to claim 19, characterized in that, the first initiator is an azo thermal initiator, a peroxide thermal initiator or an ultraviolet photoinitiator. 21. The preparation method of the resin according to claim 19, characterized in that, the polymerization is thermal polymerization or ultraviolet light polymerization, the polymerization reaction temperature of the thermal polymerization is 50-150°C, and the polymerization reaction time is 0.5-8.0 h; The polymerization reaction power of the ultraviolet light polymerization is 20-200mW/cm ² , and the polymerization reaction time is 2-20min. 22. A first color-changing functional film, characterized in that it is formed by curing the resin composition according to claim 13 or 14. 23. The first color-changing functional film according to claim 22, characterized in that the first color-changing functional film is used to transform from an initial color state to at least one colored state. 24. The first color-changing functional film according to claim 23, wherein the initial color state of the first color-changing function is a colorless transparent state or a colored color state. 25. The first color-changing functional film according to claim 23, characterized in that, the coloring state of the first color-changing function is a pure color state or a superimposed color state of multiple colors. 26. A second color-changing functional film, characterized by comprising the resin according to any one of claims 1-12. 27. The second color-changing functional film according to claim 26, characterized in that the second color-changing functional film is used to transform from an initial color state to at least one colored state. 28. The second color-changing functional film according to claim 27, wherein the initial color state of the second color-changing function is a colorless transparent state or a colored color state. 29. The second color-changing functional film according to claim 27, characterized in that, the coloring state of the second color-changing function is a pure color state or a superimposed color state of multiple colors. 30. A third color-changing functional film, characterized in that it is formed by curing the resin composition according to claim 15 or 16. 31. The third color-changing functional film according to claim 30, characterized in that, the third color-changing functional film is used to transform from an initial color state to at least one colored state. 32. The third color-changing functional film according to claim 31, characterized in that, the initial color state of the third color-changing functional film is a colorless transparent state or a colored state. 33. The third color-changing functional film according to claim 31, characterized in that, the coloring state of the third color-changing functional film is a pure color state or a superimposed color state of multiple colors. 34. A color-changing functional film, characterized in that the color-changing functional film is used to transform from an initial color state to at least two colored states. 35. The color-changing functional film according to claim 34, characterized in that, the initial color state of the color-changing functional film is a colorless transparent state or a colored state. 36. The color-changing functional film according to claim 34, characterized in that, the coloring state of the color-changing functional film is a pure color state or a superimposed color state of multiple colors. 37. The color-changing functional film according to claim 34, characterized in that, the color-changing functional film comprises a resin, or the color-changing functional film is cured from a resin composition, and the resin composition comprises the resin ,in, The resin includes at least one first repeating unit and at least one second repeating unit, the at least one first repeating unit is derived from a first monomer, and the first monomer includes a fluoran-based color-changing monomer and a conductive polymer At least one of the color-changing monomers, the at least one second repeating unit is derived from a second monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group. 38. An electrochromic device, characterized in that it comprises a first electrode and a second electrode, and an electrode according to any one of claims 22 to 25 arranged between the first electrode and the second electrode the first color-changing functional film, or The second color-changing functional film according to any one of claims 26 to 29, the ion transport adhesive layer and the ion storage layer are sequentially stacked between the first electrode and the second electrode. 39. The electrochromic device according to claim 38, wherein the ion transport adhesive layer comprises an adhesive polymer containing a polar functional group or a derivative structure thereof and an ion transport material. 40. The electrochromic device according to claim 39, wherein the adhesive polymer is a polyacrylate adhesive containing polar functional groups or derivative structures thereof. 41. The electrochromic device according to claim 40, characterized in that, the electrochromic device further comprises a transition layer located at the contact interface between the second color-changing functional film and the ion transport adhesive layer, so The transition layer includes a cross-linked structure formed by cross-linking the polar functional groups in the adhesive polymer and the polar functional groups in the second color-changing functional film. 42. An electrochromic device, characterized in that it comprises a first electrode and a second electrode, and any one of claims 22 to 25 is sequentially stacked between the first electrode and the second electrode The first color-changing functional film, and/or the second color-changing functional film as described in any one of claims 26 to 29, the ion transport adhesive layer, and the first color-changing film as described in any one of claims 30 to 33 Three-color functional film. 43. The electrochromic device according to claim 42, wherein the ion transport adhesive layer comprises an adhesive polymer containing a polar functional group or a derivative structure thereof and an ion transport material. 44. The electrochromic device according to claim 43, wherein the adhesive polymer is a polyacrylate adhesive containing polar functional groups or derivative structures thereof. 45. The electrochromic device according to claim 44, wherein the electrochromic device further comprises a transition layer located at the contact interface between the ion transport adhesive layer and the second color-changing functional film, And/or another transition layer located at the contact interface between the ion transport adhesive layer and the third color-changing functional film, each of the transition layers includes a polar functional group in the adhesive polymer and the first transition layer A cross-linked structure formed by cross-linking polar functional groups in the second color-changing functional film or the third color-changing functional film. 46. An electrochromic device, characterized in that said electrochromic device is adapted to switch from an initial color state to at least two colored states. 47. The electrochromic device according to claim 46, characterized in that the initial color state of the electrochromic device is a colorless transparent state or a colored state. 48. The electrochromic device according to claim 47, characterized in that, the colored state of the electrochromic device is a pure color state or a superimposed color state of multiple colors. 49. The electrochromic device according to claim 46, characterized in that, the electrochromic device comprises a first electrode and a second electrode, and an electrode arranged between the first electrode and the second electrode The first color-changing functional film, or the second color-changing functional film, the ion transport adhesive layer and the ion storage layer arranged between the first electrode and the second electrode, wherein, The first color-changing functional film is cured from a resin composition, the second color-changing functional film includes a resin, and the resin composition includes the resin, a fifth monomer, a second initiator, and an ion transport material and an ion storage material, the fifth monomer includes a polar functional group or a derivative structure thereof; The resin includes at least one first repeating unit and at least one second repeating unit, the at least one first repeating unit is derived from a first monomer, and the first monomer includes a fluoran-based color-changing monomer and a conductive polymer At least one of the color-changing monomers, the at least one second repeating unit is derived from a second monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group. 50. The electrochromic device according to claim 49, wherein the resin further comprises at least one third repeating unit, the at least one third repeating unit is derived from a third monomer, and the third unit The body is an acrylate monomer containing a non-polar functional group or a derivative structure of the non-polar functional group. 51. The electrochromic device according to claim 49, wherein the resin further comprises at least one fourth repeat unit derived from a fourth monomer, the fourth unit The monomer includes at least one of a fluoran-based color-changing monomer, a viologen-based color-changing monomer, and a conductive polymer-based color-changing monomer, and the fourth monomer is different from the first monomer. 52. The electrochromic device according to claim 46, characterized in that, the electrochromic device comprises a first electrode and a second electrode, and is sequentially stacked between the first electrode and the second electrode Between the first color-changing functional film, and/or the second color-changing functional film, the ion transport adhesive layer, and the third color-changing functional film, wherein, The first color-changing functional film is cured from a resin composition, the second color-changing functional film includes a resin, the third color-changing functional film is cured from another resin composition, and the resin composition Including the resin, a fifth monomer, a second initiator, an ion transport material and an ion storage material, the fifth monomer includes a polar functional group or a derivative structure thereof, the other resin composition includes the resin, said fifth monomer, said second initiator and said ion storage material, The resin includes at least one first repeating unit and at least one second repeating unit, the at least one first repeating unit is derived from a first monomer, and the first monomer includes a fluoran-based color-changing monomer and a conductive polymer At least one of the color-changing monomers, the at least one second repeating unit is derived from a second monomer, and the second monomer is an acrylate monomer containing a polar functional group or a derivative structure of a polar functional group. 53. An electronic device, characterized by comprising a casing and the electrochromic device according to any one of claims 38 to 52 arranged on the casing.