阅读说明：本技术 一种基于硅氧烷修饰光致发光物质的压力敏感涂料及其制备的涂层 (Pressure sensitive paint based on siloxane modified photoluminescence and coating prepared from pressure sensitive paint ) 是由 屈小中 杨迪 汪球 栗继伟 于 2020-04-10 设计创作，主要内容包括：本发明涉及一种基于硅氧烷修饰光致发光物质的压力敏感涂料及其制备的涂层。所述压力敏感涂料包括带有甲氧基硅烷和/或乙氧基硅烷官能团的染料、任选地硅氧烷前驱体和溶剂。本发明的压力敏感涂料的涂布方式简单、可制备超薄涂层；涂层透明,适用于工作面/测试面周围空间狭小、光学成像或光学测量设备放置困难的使用环境,在配合使用透明基底或无基底的情况下,使用透明压力敏感涂层可扩大观察设备的摆放范围,方便实验装置的摆放；同时,化学键键合染料的方法能够提高涂层的光稳定性,延长涂层使用周期,甚至可提高涂层对压力的响应速度。本发明可较大的降低压力敏感涂料对模型形状、测试区域、光路布置等的限制,拓宽压力敏感涂料的应用范围。(The invention relates to a pressure sensitive paint based on siloxane modified photoluminescence and a coating prepared from the pressure sensitive paint. The pressure sensitive coating includes a dye bearing methoxysilane and/or ethoxysilane functionality, optionally a siloxane precursor, and a solvent. The coating mode of the pressure sensitive coating is simple, and an ultrathin coating can be prepared; the coating is transparent, is suitable for the use environment with narrow space around a working surface/test surface and difficult placement of optical imaging or optical measurement equipment, and can enlarge the placement range of observation equipment by using the transparent pressure sensitive coating under the condition of matching with a transparent substrate or no substrate, thereby facilitating the placement of experimental devices; meanwhile, the method for bonding the dye by chemical bonds can improve the light stability of the coating, prolong the service life of the coating and even improve the response speed of the coating to pressure. The invention can greatly reduce the limitation of the pressure sensitive coating on the shape of a model, a test area, the arrangement of a light path and the like, and broadens the application range of the pressure sensitive coating.)

1. A pressure sensitive coating, wherein the pressure sensitive coating comprises a dye bearing methoxysilane and/or ethoxysilane functionality, optionally a siloxane precursor, and a solvent.

2. The pressure sensitive coating of claim 1, wherein the dye bearing methoxysilane and/or ethoxysilane functionality comprises a ruthenium (II) complex bearing methoxysilane and/or ethoxysilane functionality or a platinum (II) complex bearing methoxysilane and/or ethoxysilane functionality.

Preferably, the ruthenium (II) complex with methoxysilane and/or ethoxysilane functional groups has a tridentate ligand structure, and is represented by the following formula 1:

wherein, ligand L₁，L₂，L₃The same or different, independently selected from at least one of bipyridine ligand, phenanthroline ligand and biphenyl phenanthroline ligand; and L is₁、L₂And L₃At least one-R' -Si (OCH)₃)₃or-R' -Si (OC)₂H₅)₃The group, R' is a linking group.

Preferably, the bipyridine ligand has a structural formula shown in formula 2 below:

in the formula 2, R are the same or different and are independently selected from-COOH or salts thereof and-NH₂Or itSalts, -H, -CH₃、-R’-Si(OCH₃)₃、-R’-Si(OC₂H₅)₃And R' is a linking group.

Preferably, the phenanthroline ligand has a structural formula shown in formula 3 below:

in the formula 3, R is selected from-COOH or salt thereof and-NH₂Or salts thereof, -H, -CH₃、-R’-Si(OCH₃)₃or-R' -Si (OC)₂H₅)₃And R' is a linking group.

Preferably, the biphenyl o-phenanthroline ligand has a structural formula shown in formula 4 below:

in the formula 4, R are the same or different and are independently selected from-COOH or salts thereof and-NH₂Or salts thereof, -H, -CH₃、-R’-Si(OCH₃)₃、-R’-Si(OC₂H₅)₃And R' is a linking group.

Preferably, the platinum (II) complex with the methoxysilane and/or ethoxysilane functional group is a porphyrin compound serving as a ligand. Specifically, the platinum (II) complex with the methoxysilane and/or ethoxysilane functional group has a structural formula shown as the following formula 5:

in the formula 5, X are the same or different and are independently selected from-COOH or salts thereof and-NH₂Or salts thereof, -H, -CH₃Phenyl, fluorophenyl, carboxyphenyl, aminophenyl, -R' -Si (OCH)₃)₃、-R’-Si(OC₂H₅)₃X 'represents a linking group and contains at least one-R' -Si (OCH)₃)₃or-R' -Si (OC)₂H₅)₃。

Preferably, R' is a linking group of the ligand precursor to methoxysilane or ethoxysilane, for example selected from-CO-NH-, -COO-, -NH-CO-NH-, -NH-CH₂-CH(OH)-。

3. The pressure sensitive coating of claim 1 or 2, wherein the siloxane precursor is selected from Tetraethylorthosilicate (TEOS), Methyltriethoxysilane (MTES), methyltrimethoxysilane (MTMS), or an organosiloxane (directly usable or incorporable), silicone resin (directly usable or incorporable).

Preferably, the coating may further contain any photoluminescent material having no correlation between photoluminescent intensity and oxygen molecule concentration or oxygen partial pressure, and having methoxysilane and/or ethoxysilane.

4. Pressure sensitive coating according to any of claims 1 to 3, wherein the siloxane precursor is present in the coating in an amount of 0-90 wt%, preferably 35-50 wt%;

the content of the solvent in the coating is more than or equal to 10 wt% and less than 100 wt%, preferably 45-60 wt%;

the content of the dye with the methoxysilane and/or ethoxysilane functional group is more than 0 and less than or equal to 20 wt%, and preferably 0.005-0.5 wt%.

5. A pressure sensitive coating comprising the pressure sensitive paint of any one of claims 1-4.

Preferably, the pressure-sensitive coating is prepared by a coating method, for example, the pressure-sensitive coating is prepared by a method of applying the pressure-sensitive paint on the surface of a substrate.

6. A method of making a pressure sensitive coating according to claim 5, said method comprising the steps of:

and (3) coating the pressure sensitive coating on the surface of a substrate, and curing to prepare the coating.

7. The method of preparing a pressure sensitive coating according to claim 6, the method comprising the steps of:

(1) mixing a dye with methoxysilane and/or ethoxysilane functional groups, an optional siloxane precursor and a solvent, aging, coating the aged sol on the surface of a substrate, and curing to prepare the coating; alternatively, the first and second electrodes may be,

(2) mixing a siloxane precursor and a solvent, aging, coating the aged sol on the surface of a substrate, curing to obtain a bottom layer, mixing a dye with a methoxysilane and/or ethoxysilane functional group and the solvent, and coating the mixture on the surface of the bottom layer to prepare the coating.

8. Use of a pressure sensitive coating according to claim 5 for non-contact real-time measurement of the pressure and/or surface pressure distribution at the surface of a pressure sensitive coating.

Preferably, the device is used for detecting the surface pressure of one side of the coating layer and the other side of the coating layer through optical equipment, such as non-contact real-time surface pressure measurement of the surface of a model to be measured, the surface of an internal flow channel, the inside of a gap flow and the like.

9. A method for non-contact real-time measurement of pressure and/or surface pressure distribution, wherein the method comprises the steps of:

coating the pressure sensitive paint on the surface of an object to be measured to obtain a coating, irradiating the coating by an excitation light source, and taking the photoluminescence characteristic of the coating on the surface of the object to be measured by an optical recording device, so as to obtain the pressure and/or pressure distribution and the dynamic change of the pressure and/or pressure distribution of the surface of the object to be measured and the coating; alternatively, the first and second electrodes may be,

the coating is irradiated by an excitation light source, and the photoluminescence characteristic of the back surface of the surface coating of the object to be measured is shot by an optical recording device, so that the pressure and/or pressure distribution of the object to be measured and the surface of the coating of the object to be measured and the dynamic change of the pressure and/or pressure distribution are obtained, and the non-contact real-time measurement of the pressure and/or surface pressure distribution is realized.

10. The method according to claim 9, wherein the surface of the object to be measured can be any surface requiring non-contact real-time measurement, such as a surface of a model to be measured, a surface of an internal flow channel, and an internal part of a gap flow.

Technical Field

The invention relates to the field of pressure sensitive paint and coating preparation, in particular to pressure sensitive paint based on siloxane modified photoluminescence and a coating prepared from the pressure sensitive paint.

Background

Pressure Sensitive Paints (PSPs) and coatings produced therefrom are continuously being developed with improvements in the field of application of contactless surface pressure distribution measurements, the mechanism of their sensing of pressure being interpreted as the quenching of the photoluminescence of oxygen-sensitive dyes in the coating by the oxygen component of the surrounding gas. The pressure sensitive paint and the coating technology can directly shoot the image of the surface of the coating under the exciting light, the emitted light intensity or the fluorescence/phosphorescence service life and other signals by means of an optical recording device, and capture the information of the pressure distribution, the change and the like of the surface of the coating.

The fixing mode of the photoluminescence material in the PSP forming coating mainly comprises three fixing modes of physical compounding, electrostatic adsorption and chemical covalent bond fixing, wherein the covalent bond fixing can solve the problems of dye migration and leaching in a matrix and can also improve the light stability. The covalent fixation of the dye can be achieved by synthesis of the photoluminescent polymer or by in situ chemical reaction of the dye with reactive functional groups with surface functional groups of the resin matrix or coated surface.

Known work on the preparation of pressure sensitive coatings using PSPs has focused primarily on their use for the direct acquisition of optical images or optical signals of the tested surface of the coating, i.e., a surface with pressure variations.

Disclosure of Invention

In order to overcome the defects of the prior art on the transparency and the optical stability of the pressure-sensitive coating, the invention provides a pressure-sensitive coating based on siloxane modified photoluminescence and a coating prepared by the pressure-sensitive coating, wherein the pressure-sensitive coating comprises a dye with methoxysilane and/or ethoxysilane functional groups, an optional siloxane precursor and a solvent, and the transparent pressure-sensitive coating can be obtained by using the coating through a coating means; the dye with the methoxysilane and/or ethoxysilane functional group in the coating can react with a siloxane precursor to form a silicon-oxygen bond, or react with or physically adsorb active functional groups existing on the coated surface (substrate), so that the dye with the methoxysilane and/or ethoxysilane functional group is dispersed in a silicon-based coating formed on the coated surface (substrate) through chemical bond bonding, or is directly fixed on the coated surface (substrate) through chemical bond or in a physical adsorption mode, and the transparency and the optical stability of the coating are improved. The dye with the methoxysilane and/or ethoxysilane functional groups is an oxygen concentration sensitive dye, and the luminous intensity of the dye is related to the concentration of ambient oxygen molecules or the partial pressure of oxygen based on an oxygen quenching mechanism, so that the change of ambient pressure can be reflected by a light intensity signal. More particularly, the transparent coating prepared by the pressure-sensitive coating can be used for meeting the test requirement on the pressure distribution and change of the coating surface, namely a pressure test surface, by means of back-shooting imaging or back-shooting optical measurement, namely image or optical signal shooting from the non-pressure-change surface (the back surface of the coating) of the coating when an optical detection device cannot be installed or arranged in the space on one side of the coating surface. The necessary condition for realizing the shooting of the optical image information or optical signal reflecting the front surface of the coating from the back surface of the coating is that the coating has certain light transmittance. Therefore, the pressure-sensitive coating obtained by the pressure-sensitive coating has better optical transparency and oxygen permeability, and the emission intensity of the coating is related to the surface pressure of the coating. The pressure-sensitive coating and the pressure-sensitive coating prepared by the coating can be used for realizing the detection of pressure, can also be applied to the detection of the pressure change surface side by optical measurement of the non-pressure change surface or interface side of the coating, and can be used for non-contact optical characterization of the pressure of areas such as the surface of an internal flow channel, the inside of a gap flow and the like in aerodynamic research.

The purpose of the invention is realized by the following technical scheme:

a pressure sensitive coating comprising a dye bearing methoxysilane and/or ethoxysilane functionality, optionally a siloxane precursor and a solvent.

According to the invention, the dyes carrying methoxysilane and/or ethoxysilane functional groups comprise ruthenium (II) complexes carrying methoxysilane and/or ethoxysilane functional groups or platinum (II) complexes carrying methoxysilane and/or ethoxysilane functional groups.

According to the invention, the ruthenium (II) complex with methoxysilane and/or ethoxysilane functional groups has a tridentate ligand structure, and is represented by the following formula 1:

wherein, ligand L₁，L₂，L₃The same or different, independently selected from at least one of bipyridine ligand, phenanthroline ligand and biphenyl phenanthroline ligand; and L is₁、L₂And L₃At least one-R' -Si (OCH)₃)₃or-R' -Si (OC)₂H₅)₃The group, R' is a linking group.

Specifically, the bipyridine ligand has a structural formula shown as the following formula 2:

in the formula 2, R are the same or different and are independently selected from-COOH or salts thereof and-NH₂Or salts thereof, -H, -CH₃、-R’-Si(OCH₃)₃、-R’-Si(OC₂H₅)₃And R' is a linking group.

Specifically, the phenanthroline ligand has a structural formula shown as the following formula 3:

in the formula 3, R is selected from-COOH or salt thereof and-NH₂Or salts thereof, -H, -CH₃、-R’-Si(OCH₃)₃or-R' -Si (OC)₂H₅)₃And R' is a linking group.

Specifically, the biphenyl o-phenanthroline ligand has a structural formula shown as the following formula 4:

in the formula 4, R are the same or different and are independently selected from-COOH or salts thereof and-NH₂Or salts thereof, -H, -CH₃、-R’-Si(OCH₃)₃、-R’-Si(OC₂H₅)₃And R' is a linking group.

According to the invention, the platinum (II) complex with methoxysilane and/or ethoxysilane functional groups is a porphyrin compound serving as a ligand. Specifically, the platinum (II) complex with the methoxysilane and/or ethoxysilane functional group has a structural formula shown as the following formula 5:

in the formula 5, X are the same or different and are independently selected from-COOH or salts thereof and-NH₂Or salts thereof, -H, -CH₃Phenyl, fluorophenyl, carboxyphenyl, aminophenyl, -R' -Si (OCH)₃)₃、-R’-Si(OC₂H₅)₃X 'represents a linking group and contains at least one-R' -Si (OCH)₃)₃or-R' -Si (OC)₂H₅)₃。

According to the invention, R' is a ligand parent and methoxysilane or ethylLinking groups of oxysilanes, e.g. selected from-CO-NH-, -COO-, -NH-CO-NH-, -NH-CH₂-CH(OH)-。

According to the invention, the siloxane precursor is selected from tetraethyl orthosilicate (TEOS), Methyltriethoxysilane (MTES), methyltrimethoxysilane (MTMS), or an organosiloxane (which can be used or incorporated directly), a silicone resin (which can be used or incorporated directly), such as polydimethylsiloxane PDMS, room temperature vulcanizing silicone rubber RTV.

According to the present invention, the solvent is selected from water, an organic solvent, or a mixed solvent of water and an organic solvent; preferably, the solvent is selected from an organic solvent or a mixed solvent of water and an organic solvent; the organic solvent is selected from ethanol, methanol, tetrahydrofuran, etc.

According to the invention, the coating material can also comprise acid or alkali, the pH value of the coating material can be adjusted by adding the acid or alkali, the acid can also be used as a catalyst, and the acid is acetic acid or hydrochloric acid.

According to the invention, the siloxane precursor is present in the coating in an amount of 0 to 90 wt.%, preferably 35 to 50 wt.%, for example 0 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%.

According to the invention, the solvent is present in the dope in an amount of 10 wt.% or more and less than 100 wt.%, preferably 45 to 60 wt.%, for example 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, 98 wt.%.

According to the invention, the amount of the dye carrying methoxysilane and/or ethoxysilane functional groups is greater than 0 and less than or equal to 20 wt%, preferably between 0.005 and 0.5 wt%, for example 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%.

According to the invention, the coating may also contain any photoluminescent material with methoxysilanes and/or ethoxysilanes, which do not have a correlation between the photoluminescent intensity and the oxygen molecule concentration or the oxygen partial pressure, in an amount of 0 to 50% by weight. For example from temperature-responsive or non-responsive dyes with methoxysilanes and/or ethoxysilanes, or from siloxane-modified carbon sites.

The invention also provides a preparation method of the pressure-sensitive coating, which comprises the following steps:

the pressure sensitive coating is prepared by mixing a dye with methoxysilane and/or ethoxysilane functional groups, optionally a siloxane precursor, and a solvent.

According to the invention, the mixing may also be followed by an aging step, for example 1 to 3 days at room temperature.

The invention also provides a pressure-sensitive coating, which comprises the pressure-sensitive paint.

According to the invention, the pressure-sensitive coating is prepared by a coating method, for example, the pressure-sensitive coating is prepared by a method of coating the pressure-sensitive coating on the surface of a substrate.

During the coating process, the dye with the methoxysilane and/or ethoxysilane functional group can react with a siloxane precursor to form a silicon-oxygen bond, or react with or physically adsorb active functional groups existing on the surface of the substrate, so that the dye with the methoxysilane and/or ethoxysilane functional group is dispersed in a silicon-based coating formed on the surface of the substrate through chemical bond bonding, or is directly fixed on the surface of the substrate through chemical bond or in a physical adsorption mode.

According to the invention, the application can be, for example, spraying, dripping, brushing, spin coating, dip-drawing, etc.

According to the invention, the pressure-sensitive coating has photoluminescent properties and the intensity of the emitted light is related to the concentration of oxygen molecules or the partial pressure of oxygen at the surface of the coating, at least at a certain wavelength.

According to the invention, the thickness of the pressure-sensitive coating is 1 to 10 μm.

According to the invention, the pressure-sensitive coating has a light transmission in the visible range of more than 40%.

The invention also provides a preparation method of the pressure sensitive coating, which comprises the following steps:

and (3) coating the pressure sensitive coating on the surface of a substrate, and curing to prepare the coating.

According to the present invention, the substrate may be glass, plastic, resin, aluminum, steel, ceramic or the above-mentioned material with hydroxyl group modified on the surface, and preferably is transparent material such as optical glass, quartz glass, organic glass or transparent substrate prepared from siloxane precursor.

Illustratively, the coating is prepared by the following method:

(1) mixing a dye with methoxysilane and/or ethoxysilane functional groups, an optional siloxane precursor and a solvent, aging, coating the aged sol on the surface of a substrate, and curing to prepare the coating; alternatively, the first and second electrodes may be,

(2) mixing a siloxane precursor and a solvent, aging, coating the aged sol on the surface of a substrate, curing to obtain a bottom layer, mixing a dye with a methoxysilane and/or ethoxysilane functional group and the solvent, and coating the mixture on the surface of the bottom layer to prepare the coating.

According to the invention, the curing time is between 0.1 and 72 hours and the curing temperature is between 0 and 90 ℃.

According to the present invention, the coating layer may be used alone in the form of a self-supporting film under the condition that the substrate is removed.

The invention also provides the application of the pressure sensitive coating, which is used for carrying out non-contact real-time measurement on the pressure and/or surface pressure distribution of the surface of the pressure sensitive coating.

According to the invention, the device is used for detecting the surface pressure of the other side of the coating from one side of the coating by optical equipment, such as non-contact real-time surface pressure measurement of the surface of a model to be measured, the surface of an internal flow channel, the inside of a gap flow and the like.

The invention also provides a method for non-contact real-time measurement of pressure and/or surface pressure distribution, comprising the following steps:

coating the pressure sensitive paint on the surface of an object to be measured to obtain a coating, irradiating the coating by an excitation light source, and taking the photoluminescence characteristic of the coating on the surface of the object to be measured by an optical recording device, so as to obtain the pressure and/or pressure distribution and the dynamic change of the pressure and/or pressure distribution of the surface of the object to be measured and the coating; alternatively, the first and second electrodes may be,

the coating is irradiated by an excitation light source, and the photoluminescence characteristic of the back surface of the surface coating of the object to be measured is shot by an optical recording device, so that the pressure and/or pressure distribution of the object to be measured and the surface of the coating of the object to be measured and the dynamic change of the pressure and/or pressure distribution are obtained, and the non-contact real-time measurement of the pressure and/or surface pressure distribution is realized.

According to the invention, the surface of the object to be measured can be any surface which needs to be measured in a non-contact real-time manner, such as the surface of a model to be measured, the surface of an inner flow passage and the inside of a gap flow.

Has the advantages that:

compared with the prior art, the pressure-sensitive coating has simple and various coating modes, and can be used for preparing ultrathin coatings by skillfully applying a coating method; the coating is transparent, is suitable for the use environment with narrow space around a working surface/test surface and difficult placement of optical imaging or optical measurement equipment, and can enlarge the placement range of observation equipment by using the transparent pressure sensitive coating under the condition of matching with a transparent substrate or no substrate, thereby facilitating the placement of experimental devices; meanwhile, the method for bonding the dye by chemical bonds can improve the light stability of the coating, prolong the service life of the coating and even improve the response speed of the coating to pressure. The invention can greatly reduce the limitation of the pressure sensitive coating on the shape of a model, a test area, the arrangement of a light path and the like, and broadens the application range of the pressure sensitive coating.

The pressure sensitive paint of the present invention has the main characteristic of allowing optical equipment to obtain the pressure distribution and dynamic change information of the surface of the coating from the back of the coating, so that the optical equipment can be used for measuring the pressure in a specific internal flow field when the pressure sensitive paint is applied to aerodynamic research.

Drawings

FIG. 1 is a graph showing the comparison of fluorescence intensity of a photoluminescent clear coating prepared in example 1 of the present invention under 470nm excitation light in air and nitrogen atmosphere.

Fig. 2 shows a photo of the photoluminescent transparent coating prepared in example 2 of the present invention under natural light, a fluorescent photo of the photoluminescent transparent coating obtained by purging a nozzle with ultraviolet light, a red light channel image in the fluorescent photo, and a pseudo-color treatment performed on the red light channel image.

FIG. 3 is a graph showing the change of fluorescence intensity with time under continuous irradiation of excitation light for the photoluminescent transparent coating layer prepared in example 3 of the present invention.

Fig. 4 shows the light intensity change of the pressure-responsive photoluminescent transparent coating prepared in example 4 of the present invention after pseudo-color treatment in a shock tube test.

Detailed Description

The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.

Example 1

According to The reference [ Wang Z, Mcwilliams A R, Evans C E B, et al, solvent Attachment of RuII phenolic Compounds to Polymeric Compounds [ The Development and Evaluation of Single-Component Polymeric Oxygen Sensors [ J].Advanced Functional Materials,2002,12(6-7):415-419.]Preparation of bis (4, 7-diphenyl-1, 10-phenanthroline dichloride) - (4, 4' -dicarboxy-bipyridine) ruthenium (II) complex [ Ru (bphen)₂(dcbpy)]²⁺]Cl₂。

Preparing an ethoxysilane modified Ru complex Ru-KH 550: will [ Ru (bphen) ]₂(dcbpy)]²⁺]Cl₂Dissolved in excess anhydrous SOCl₂In (4mL), the mixture was refluxed for 6 hours, and SOCl was evaporated under reduced pressure₂And the residue was reacted with KH550 under nitrogen in ice bath and then at room temperature in the presence of excess anhydrous pyridine at room temperature, wherein n ([ Ru (bphen))₂(dcbpy)]²⁺]Cl₂) N (KH550) was filtered after 12 hours at 1:2, and the remaining organic solvent was evaporated to give Ru-KH550, an ethoxysilane-modified Ru complex.

Preparing the photoluminescent clear coating by a premixing method: uniformly mixing Methyl Triethoxysilane (MTES) and ethanol at a volume ratio of 2:5 (total volume of 30mL), adding 1mL ethanol solution of Ru-KH550 with concentration of 1.5mg/mL, adding appropriate amount of acetic acid as catalyst into the mixed solution, adjusting pH to about 5, and stirring at room temperature for aging for 3 days.

Preparing a pressure-responsive photoluminescent transparent coating: and brushing the aged sol on a transparent glass plate subjected to surface hydroxylation treatment, and curing the coating at 80 ℃ for 12 hours to obtain a transparent bottom layer with the thickness of about 2 microns.

Oxygen responsiveness test: the fluorescence spectrum of the Ru-KH550 oxygen concentration sensitive transparent coating is measured by using excitation light with the wavelength of 470nm, nitrogen is introduced into a measured sample, and the oxygen concentration responsiveness is observed. FIG. 1 shows the fluorescence emission spectrum of an oxygen concentration responsive transparent coating under 470nm excitation light, and the oxygen concentration responsiveness was observed comparing the fluorescence emission intensity of the coating in air as well as in nitrogen. The light intensity of the clear coating in nitrogen was found to be much higher than that in air, about 2 times that in air, indicating that the coating has a significant response to changes in oxygen concentration.

Example 2

An ethoxysilane-modified Ru complex Ru-KH550 was prepared by the same method as in example 1.

Preparing a photoluminescent clear coating by a two-layer method:

1) preparing a transparent bottom layer: uniformly mixing Methyl Triethoxysilane (MTES) and an ethanol solvent in a volume ratio of 2:5, adding a proper amount of acetic acid as a catalyst into the mixed solution, adjusting the pH value to about 5, stirring at room temperature for aging for 2 days, spraying the aged precursor onto a transparent glass plate with the surface subjected to hydroxylation treatment, wherein the diameter of a nozzle is 0.8 mm, placing the coating at 80 ℃, and curing for 6 hours to obtain a transparent bottom layer.

2) Preparing a pressure-responsive photoluminescent transparent coating: spraying 1.5mg/mL ethanol solution of Ru-KH550 on the transparent bottom layer, heating in dark place, and washing off unreacted Ru-KH550 on the surface with ethanol to obtain a coating with thickness of about 2 μm.

Oxygen responsiveness test: blowing nitrogen to a transparent position through a nozzle with the caliber of about 2mm, observing the light emitting condition of the coating under ultraviolet excitation light, recording the change of the coating by using a camera, then carrying out channel segmentation treatment on the color picture to obtain a red light channel image, and simultaneously carrying out pseudo-color treatment coloring on the red light channel image to compare the difference between the nitrogen blowing position and the non-blowing position under the red channel. The pictures in fig. 2 show from left to right a photograph of the clear coat in natural light, a fluorescent photograph of blowing the nozzle over the clear coat under ultraviolet illumination, a red light channel map in the fluorescent photograph, and a pseudo-color treatment of the red light channel photograph. The red light luminous intensity of the oxygen concentration sensitive probe Ru at the nitrogen purging position is found to be brighter than the red light at the surrounding non-purging position, which shows that the transparent coating system has obvious response to the change of the oxygen concentration and can effectively detect the change of the air pressure.

Example 3

According to the reference [ Suzanne, Belanger, Keith, et al].Langmuir,1999,15,837-843]Preparation of bis (4, 7-diphenyl-1, 10-phenanthroline) - (5-amino-1, 10-phenanthroline) ruthenium (II) dichloride complex [ Ru (bphen)₂(NH₂-phen)]²⁺]Cl₂。

Preparing a silane coupling agent-Ru complex Ru-KH 560: will [ Ru (bphen) ]₂(NH₂-phen)]²⁺]Cl₂Reacting with gamma-glycidoxypropyltrimethoxysilane KH560 at a molar ratio of n (Ru) to n (KH560) of 1:1 in methanol as solvent,the reaction was carried out for 12h at 65 ℃ in the absence of light and the solvent was removed by evaporation at low pressure.

Preparing the photoluminescent clear coating by a premixing method: mixing Methyl Triethoxysilane (MTES) and ethanol at a volume ratio of 1:2 (total volume of 30mL), adding 1mL of 3mg/mL Ru-KH560 ethanol solution, adding appropriate amount of acetic acid as catalyst, adjusting pH to about 4, and stirring at room temperature for aging for 2 days.

Preparing a pressure-responsive photoluminescent transparent coating: and spin-coating the aged sol on a transparent glass plate subjected to surface hydroxylation treatment, placing the coating at 80 ℃, and curing for 12 hours to obtain a transparent bottom layer, wherein the thickness of the coating is about 2 mu m.

Photobleaching test: the clear coating Ru-KH560 was tested for photobleaching resistance. The clear coat layer was continuously irradiated with 470nm excitation light for 2000s, wherein the excitation light power at the coating layer was measured with an optical power meter to be about 2mW, and the change in light intensity at 600nm of the coating layer was captured by a fluorescence spectrometer, as shown in fig. 3, the clear coat system showed no decrease in light intensity under continuous illumination and a photobleaching rate of 0.1%/h.

Example 4

According to the reference [ Suzanne, Belanger, Keith, et al].Langmuir,1999,15,837-843]Preparation of tris (5-amino-1, 10-phenanthroline) ruthenium bis hexafluorophosphate complex Ru (NH)₂-phen)₃(PF₆)₂。

Preparing a silane coupling agent-Ru complex Ru-KH 560: ru (NH)₂-phen)₃(PF₆)₂Reacting with gamma-glycidoxypropyltrimethoxysilane KH560 at a molar ratio of n (Ru) to n (KH560) of 1:3, reacting with methanol at 65 deg.C in the dark for 12h, and evaporating to remove the solvent under low pressure.

Preparing a transparent bottom layer: mixing Methyl Triethoxysilane (MTES) and tetraethoxysilane TEOS according to a volume ratio of 4:1 (the total volume is 50mL), adding 30mL ethanol as a solvent, adding a proper amount of acetic acid as a catalyst into the mixed solution, adjusting the pH value to about 5, stirring at room temperature for aging for 2 days, spraying the aged precursor onto a transparent glass plate with the surface subjected to hydroxylation treatment, wherein the diameter of a nozzle is 0.8 mm, placing the coating at 80 ℃, and curing for 6 hours to obtain a transparent bottom layer.

Preparing a pressure concentration response photoluminescence transparent coating: an ethanol solution (6mg/mL) of ruthenium (Ru-KH560) modified by a silane coupling agent was sprayed on the transparent bottom layer, and the transparent bottom layer was heated away from light, and then unreacted Ru-KH560 on the surface was washed off with ethanol to obtain a coating of about 3 μm in thickness.

Oxygen responsiveness test: the fluorescence spectrum of the Ru-KH560 oxygen-sensitive coating was measured by using excitation light with a wavelength of 470nm, and the oxygen concentration responsiveness was observed by introducing nitrogen gas to the sample to be measured.

And (3) pressure response test: and testing the pressure response speed of the transparent coating by means of equipment such as a shock tube, a high-speed camera and the like. The method comprises the steps of fixing a transparent coating in a shock tube, irradiating a coating sample through a glass window with the diameter of 12cm under ultraviolet excitation light (365nm), enabling the coating to be located in a low-pressure section of the shock tube, dividing the shock tube into a low-pressure section and a high-pressure section through a diaphragm, pumping gas in the low-pressure section by using a vacuum pump, continuously and slowly pressurizing the high-pressure section through an air pump, breaking the diaphragm when a certain pressure value is reached, enabling high-pressure air to rapidly enter the low-pressure section, triggering a high-speed camera to take pictures after the high-pressure air flows to the low-pressure section, synchronously acquiring air pressure changes by an acquisition system, seeing the change of the fluorescence intensity of the coating of the sample by combining pictures taken by the high-speed camera, and judging the response time of the coating to the change of oxygen partial pressure by combining with the capturing time of the acquisition system.

FIG. 4 shows that the red channel of the photographs at different times was pseudo-colored, the airflow started to reach the coating after 837.5 μ s, and the brightness of the coating decreased significantly after 25 μ s, indicating that the response time of the coating was about 25 μ s.

Example 5

According to the reference [ Suzanne, Belanger, Keith, et al].Langmuir,1999,15,837-843]Preparation of bis (5-amino-1, 10-phenanthroline) - (2, 2' -bipyridine) ruthenium (II) dichloride complex [ Ru (NH)₂-phen)₂(bpy)]²⁺]Cl₂。

Preparing a methoxysilane-Ru complex: will [ Ru (NH)₂-phen)₂(bpy)]²⁺]Cl₂Reacting with 3-isocyanatopropyl trimethoxy silane in a feeding molar ratio of n (Ru) to n (methoxy silane) of 1:2, reacting for 12 hours in a nitrogen atmosphere at 65 ℃ in the dark by taking tetrahydrofuran as a solvent, and evaporating to remove the solvent under low pressure.

Preparing a pressure-responsive photoluminescent transparent coating: directly spraying an ethanol solution (5mg/mL) of the methoxysilane-Ru complex onto a glass sheet with the surface subjected to hydroxylation treatment, curing at 80 ℃, and washing with ethanol for multiple times to obtain the pressure-sensitive transparent coating.

And (3) carrying out a pressure response test on the coating, and testing the pressure response speed of the transparent coating by means of equipment such as a shock tube, a high-speed camera and the like. Fixing a transparent coating in a shock tube, irradiating a coating sample through a glass window with the diameter of 12cm under ultraviolet excitation light (365nm), wherein the coating is positioned at a low-pressure section of the shock tube, dividing the shock tube into the low-pressure section and a high-pressure section through a diaphragm, pumping gas in the low-pressure section by using a vacuum pump, continuously and slowly pressurizing the high-pressure section through an air pump, breaking the diaphragm when a certain pressure value is reached, rapidly enabling high-pressure air to enter the low-pressure section, triggering a high-speed camera to take a picture after the high-pressure air flows to the low-pressure section, synchronously acquiring the air pressure change by an acquisition system, judging the response time of the coating to the oxygen partial pressure change by combining the above technologies, and displaying the response time of the coating to the oxygen partial pressure change to be about 24 mu s.

Example 6

According to the reference [ Suzanne, Belanger, Keith, et al].Langmuir,1999,15,837-843]Preparation of bis (5-amino-1, 10-phenanthroline) - (2, 2' -bipyridine) ruthenium (II) dichloride complex [ Ru (NH)₂-phen)₂(bpy)]²⁺]Cl₂。

Preparing a methoxysilane-Ru complex: will [ Ru (NH)₂-phen)₂(bpy)]²⁺]Cl₂Reacting with 3-isocyanatopropyl trimethoxy silane in the molar ratio of n (Ru) to n (methoxy silane) of 1:2, taking tetrahydrofuran as a solvent and keeping out of the sun by 6 percentThe reaction was carried out at 5 ℃ for 12h under a nitrogen atmosphere and the solvent was removed by evaporation at low pressure.

Preparing the photoluminescent clear coating by a premixing method: mixing Methyl Triethoxysilane (MTES) and ethanol at a volume ratio of 1:1 (total volume of 20mL), adding 1mL of 2mg/mL methoxysilane-Ru tetrahydrofuran solution, adding appropriate amount of acetic acid as catalyst, adjusting pH to about 4, and stirring at room temperature for aging for 2 days.

Preparing a pressure-responsive photoluminescent transparent coating: and dripping the aged sol on a stainless steel sheet, placing the coating at 80 ℃, and curing for 12 hours to obtain a transparent bottom layer with the thickness of about 4 mu m.

Photobleaching test: the clear coating Ru-KH560 was tested for photobleaching resistance. The transparent coating was continuously irradiated with excitation light at 470nm for 2000s, wherein the excitation light power at the coating was measured with an optical power meter to be about 2mW, and the change in light intensity at 600nm of the coating was captured by a fluorescence spectrometer.

Example 7

5- (4-carboxyphenyl) -10,15, 20-triphenylporphyrin platinum was prepared according to the reference [ Synthesis of poly (isobutyl-co-2,2, 2-trifluoromethylmethyl methacrylate) with 5,10,15, 20-tetraphenylphosphinate platinum (II) molar as an oxidative-sensing dye for pressure-sensing patent [ J ]. Journal of Polymer Science Part A: Polymer Chemistry,2005,43(14) ].

Preparing an ethoxysilane modified Pt complex: dissolving 5- (4-carboxyphenyl) -10,15, 20-triphenylporphyrin platinum in excess anhydrous SOCl₂In (4mL), the mixture was refluxed for 6 hours, and SOCl was evaporated under reduced pressure₂And reacting the residue with KH550 under nitrogen at room temperature in the presence of excess anhydrous pyridine, firstly carrying out ice bath reaction and then room temperature reaction, wherein n (Pt) n (ethoxysilane) is 1:1, filtering after 12 hours, and evaporating the residual organic solvent to obtain the ethoxysilane modified Pt complex Pt-KH 550.

Preparing the photoluminescent clear coating by a premixing method: methyl Triethoxysilane (MTES), TEOS and ethanol were mixed at a volume ratio of 2:1:2 (total volume 100mL), 3mL of a 5mg/mL Pt-KH550 tetrahydrofuran solution was added, an appropriate amount of acetic acid was added to the mixed solution as a catalyst, and the pH was adjusted to about 4, followed by aging for 2 days with stirring at room temperature.

Preparing a pressure-responsive photoluminescent transparent coating: and (3) preparing the aged sol film on a transparent glass plate subjected to surface hydroxylation treatment by a dip-coating method, and curing the coating at 80 ℃ for 12 hours to obtain a transparent bottom layer with the thickness of about 2 microns.

The transparent coating is subjected to a back shooting imaging test, namely an excitation light source and a camera are placed on the back of the transparent coating, nitrogen is blown to the front of the coating through a nozzle with the caliber of about 2mm, and the light-emitting condition of the back of the coating is observed under ultraviolet excitation light, so that the position of the coating blown by the nitrogen is obviously brighter than the surrounding un-blown position. And performing channel segmentation processing on the obtained picture by using software to obtain a red light channel image, and performing pseudo-color processing coloring on the red light channel image to compare the difference between the nitrogen purging position and the non-purging position under the red channel. The red light emission intensity at the nitrogen purge is found to be brighter than that at the ambient un-purged region, indicating that the transparent coating system has obvious response to the change of the oxygen concentration and the transparency of the transparent coating system can meet the requirements of the back-up imaging.

Example 8

5- (4-aminophenyl) -10,15, 20-triphenylporphyrin platinum was prepared according to the reference (Synthesis of poly (isobutyl-co-2,2, 2-trifluoromethylmethacrylate) with 5,10,15, 20-tetraphenylphosphinate platinum (II) molar as an oxidative-sensing dye for pressure-sensing patent [ J ]. Journal of Polymer Science Part A: Polymer Chemistry,2005,43 (14)).

Preparing a methoxysilane modified Pt complex: reacting 5- (4-aminophenyl) -10,15, 20-triphenylporphyrin platinum with 3-isocyanate propyl trimethoxy silane at a feeding molar ratio of n (Pt) to n (3-isocyanate propyl trimethoxy silane) of 1:1, reacting for 12 hours in a nitrogen atmosphere at 65 ℃ in the dark by taking tetrahydrofuran as a solvent, and evaporating the solvent at low pressure.

Preparing a photoluminescent clear coating by a two-layer method:

1) preparing a transparent bottom layer: uniformly mixing Methyl Triethoxysilane (MTES) and an ethanol solvent in a volume ratio of 2:5 (the total volume is 140mL), adding a proper amount of acetic acid as a catalyst into the mixed solution, adjusting the pH value to about 5, stirring at room temperature for aging, spraying the aged precursor onto a transparent glass plate with the surface subjected to hydroxylation treatment, wherein the diameter of a nozzle is 0.8 mm, placing the coating at 80 ℃, and curing for 6 hours to obtain a transparent bottom layer.

2) Preparing a pressure-responsive photoluminescent transparent coating: the tetrahydrofuran solution of platinum modified by methoxysilane with the concentration of 10mg/mL is sprayed on the transparent bottom layer, and is heated in the dark, and then unreacted silane dye on the surface is washed away by tetrahydrofuran, and the thickness of the coating is about 3 mu m.

And (3) carrying out a pressure response test on the coating, and testing the pressure response speed of the transparent coating by means of equipment such as a shock tube, a high-speed camera and the like. Fixing a transparent coating in a shock tube, irradiating a coating sample through a glass window with the diameter of 12cm under ultraviolet excitation light (365nm), wherein the coating is positioned at a low-pressure section of the shock tube, dividing the shock tube into the low-pressure section and a high-pressure section through a diaphragm, pumping gas in the low-pressure section by using a vacuum pump, continuously and slowly pressurizing the high-pressure section through an air pump, breaking the diaphragm when a certain pressure value is reached, rapidly enabling high-pressure air to enter the low-pressure section, triggering a high-speed camera to take a picture after the high-pressure air flows to the low-pressure section, synchronously acquiring the air pressure change by an acquisition system, judging the response time of the coating to the oxygen partial pressure change by combining the above technologies, and displaying the response time of the coating to the oxygen partial pressure change to be about 24 mu s.

Example 9

5,10, 15-tris- (2,3,4,5, 6-pentafluorophenyl) -20- (2,3,4, 5-tetrafluoro-6-phenylacetic acid) -porphyrin platinum was prepared according to the reference (Tian, Yanqing, Shumway, Bradley R, Meldrum, deirde R.A new cross-linked oxo sensor co-valent bonded into poly (2-hydroxyhexyl methacrylate) -co-polyarylamide film for dissolved oxo sensing [ J ] Chemistry of Materials,22(6):2069 and 2078).

Preparing an ethoxysilane modified Pt complex: dissolving 5,10, 15-tris- (2,3,4,5, 6-pentafluorophenyl) -20- (2,3,4, 5-tetrafluoro-6-phenylacetic acid) -porphyrin platinum in excess anhydrous SOCl₂In (4mL), the mixture was refluxed for 6 hours, and SOCl was evaporated under reduced pressure₂And the residue is brought to room temperatureReacting KH550 with anhydrous pyridine under nitrogen at room temperature, reacting at room temperature, filtering after 12h, and evaporating residual organic solvent to obtain Pt-KH550 modified by ethoxysilane.

Blue fluorescent carbon dot layers with silane-modified bottoms were prepared according to the reference [ Di, Yang, et al.construction of bi-layer bi-luminescent surface-reforming sensitive coating for non-contact homogeneous Testing [ J ]. Polymer Testing,2019,105922 ], and pressure sensitive coatings were prepared on top by a pre-mix method.

Preparing the photoluminescent clear coating by a premixing method: uniformly mixing Methyl Triethoxysilane (MTES) and ethanol solvent at a volume ratio of 2:5 (the total volume is 140mL), adding 5mL of 5mg/mL Pt-KH550 tetrahydrofuran solution, adding appropriate amount of acetic acid as catalyst into the mixed solution, adjusting pH to about 3, and stirring at room temperature for aging for 1 day.

Preparing a pressure-responsive photoluminescent transparent coating: and spraying the aged sol onto a blue fluorescent carbon dot layer, wherein the diameter of a nozzle is 0.8 mm, placing the coating at 80 ℃, and curing for 12 hours to obtain the double-probe self-reference pressure sensitive transparent coating, wherein the thickness of the coating is about 2 mu m.

And (3) carrying out a pressure response test on the coating, and testing the pressure response speed of the transparent coating by means of equipment such as a shock tube, a high-speed camera and the like. Fixing a transparent coating in a shock tube, irradiating a coating sample through a glass window with the diameter of 12cm under ultraviolet excitation light (365nm), wherein the coating is positioned at a low-pressure section of the shock tube, dividing the shock tube into the low-pressure section and a high-pressure section through a diaphragm, pumping gas in the low-pressure section by using a vacuum pump, continuously and slowly pressurizing the high-pressure section through an air pump, breaking the diaphragm when a certain pressure value is reached, rapidly enabling high-pressure air to enter the low-pressure section, triggering a high-speed camera to take a picture after the high-pressure air flows to the low-pressure section, synchronously acquiring the air pressure change by an acquisition system, judging the response time of the coating to the oxygen partial pressure change by combining the above technologies, and displaying the response time of the coating to the oxygen partial pressure change to be about 27 mu s by a result.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.