POSS modified monomer as well as preparation method and application thereof

Abstract

The invention belongs to the field of high polymer materials, and discloses a POSS (Polyhedral Oligomeric Silsesquioxane) modified monomer as well as a preparation method and application thereof. According to the POSS modified monomer, a vinyl POSS (T8-POSS) basic framework with a T8 structure is adopted, a hydrophobic perfluoroalkyl chain (SF) and a thermosensitive benzocyclobutenyl (Si-B) unit are introduced to an inorganic cage, when the POSS modified monomer is subjected to thermocuring to form a multifunctional coating, a hybrid network structure can be constructed by adjusting the content of the SF and the content of the Si-B unit, and therefore the multifunctional coating is formed. The effects of controlling the optical, mechanical, thermal and surface wettability of the coating are achieved, and the coating has high mechanical strength and environment barrier efficiency. Meanwhile, the invention also discloses a preparation method of the POSS modified monomer and a coating prepared from the POSS modified monomer.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a POSS-modified monomer, its preparation method, and its application as a coating material in flexible devices. Background Technology

[0002] Flexible optoelectronic devices, such as organic light-emitting diodes (OLEDs), have broken through the spatial limitations of traditional rigid electronic devices due to their ability to be bent, folded, or adhere to complex curved surfaces, demonstrating enormous application potential in emerging technology fields such as wearable devices and foldable displays. These devices are designed to be extremely thin and light to improve mechanical flexibility and compliance, thereby reducing the risk of functional failure caused by bending stress. However, this design strategy often sacrifices several important functions, including hydrophobicity, mechanical strength, and chemical resistance. Furthermore, the key materials of these flexible devices are often fragile, not only vulnerable to external mechanical damage but also highly sensitive to moisture and oxygen. Long-term exposure to corrosive environments can easily lead to irreversible chemical reactions such as oxidation and corrosion, resulting in performance degradation and even eventual device failure. An ideal protection strategy needs to be built from the interface layer where the device contacts the environment. This requires the outermost layer to not only act as a physical barrier against mechanical impact but also to simultaneously block environmental erosion such as water and oxygen. Therefore, developing an integrated multifunctional protective coating that combines high mechanical strength with environmental barrier efficiency is of great significance.

[0003] Currently, protective coatings for flexible devices are mainly divided into two categories, but both have performance bottlenecks. One category is based on inorganic materials, such as silicon oxide (SiO2) and silicon nitride (Si3N4). These materials have a highly dense, strongly bonded network structure, which can effectively resist external mechanical stress and block moisture and oxygen. However, their inherent rigidity makes them unable to withstand the stress generated during repeated bending or folding of flexible devices, and they are prone to microcracks or even peeling off the entire device surface. Moreover, the poor transparency of these materials also hinders their application in the optoelectronic display field. The other category is flexible layers based on organic materials, such as polyurethane (PU) and polyimide (PI). These materials have good flexibility and can adapt to complex bending or folding deformation requirements. However, due to their inherent molecular structure characteristics, such as the large free volume between chain segments and the weak interaction forces between molecular chains, they are difficult to form a dense barrier that prevents water vapor and oxygen from passing through.

[0004] Polysilsesquioxanes (POSS), as nanoscale "molecular building blocks," possess a rigid Si-O-Si inorganic core that provides excellent mechanical strength and chemical stability, while modifiable organic substituents on the cage can endow the material with flexibility and other customized functions. This makes it possible to resolve the inherent contradiction between hardness and flexibility at the molecular level. Although significant progress has been made in the research of POSS-based coatings that are both flexible and hard, studies that simultaneously possess excellent water and oxygen barrier properties are rarely reported. This phenomenon may be related to the fact that existing research mainly uses POSS mixture systems, and the uncertainty of the system structure and composition of this system can lead to performance mismatch. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a POSS-modified monomer whose coating possesses both high mechanical strength and environmental barrier efficiency. Furthermore, this invention also provides a method for preparing the POSS-modified monomer and its properties as a coating material.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a POSS-modified monomer, the structural formula of which is shown below:

[0007]

[0008] In the structural formula:

[0009] R is vinyl; x+y=8, where x and y are both integers or decimals greater than 0;

[0010] The SF group is the following:

[0011]

[0012] The POSS-modified monomer of this invention uses a vinyl POSS (T8-POSS) with a T8 structure as the basic framework. Through thiol-ene click reaction and hydrosilanization reaction, hydrophobic perfluoroalkyl chain (SF) and thermosensitive benzocyclobutenyl (Si-B) units are introduced into its inorganic cage. When the obtained POSS-modified monomer is thermocured to form a multifunctional coating, the hybrid network structure is constructed by adjusting the content of SF and Si-B units, thereby achieving control over the optical, mechanical, thermal and surface wetting properties of the coating.

[0013] The POSS-modified monomer described in this invention is named T8B. x SF yThe x is 1-8, and the y is 0-8. The x can be any of the following values: 1, 1.2, 1.4, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.1, 4.2, 4.4, 4.5, 5, 5.2, 5.4, 5.5, 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, 7.9.

[0014] Preferably, x is 6.4 and y is 1.6. In the POSS-modified monomer, when x is 6.4 and y is 1.6, the POSS-modified monomer is named T8B. 6.4 SF 1.6 The T8B 6.4 SF 1.6 It appears as a hard, waxy solid.

[0015] Preferably, x is 5.5 and y is 2.5. When x is 5.5 and y is 2.5, the POSS-modified monomer is named T8B. 5.5 SF 2.5 The T8B 5.5 SF 2.5 It is a soft, waxy solid.

[0016] Preferably, x is 5.1 and y is 2.9. When x is 5.1 and y is 2.9, the POSS-modified monomer is named T8B. 5.1 SF 2.9 The T8B 5.1 SF 2.9 It is a viscous liquid.

[0017] Secondly, the present invention provides a method for preparing the POSS-modified monomer as described above, the method comprising the following steps:

[0018] Step (1): Take benzocyclobutene-4-dimethylsilane, octavinyl cage-type silsesquioxane and 1H,1H,2H,2H-perfluorodecylthiol respectively;

[0019] Step (2): Under a nitrogen atmosphere, add octavinyl cage-type silsesquioxane to an organic solvent and stir to dissolve. Then add 1H,1H,2H,2H-perfluorodecylthiol and photoinitiator. After stirring evenly, irradiate the reaction with a UV lamp. After the reaction is complete, remove the organic solvent, purify and dry to obtain the intermediate.

[0020] Step (3): Place the intermediate obtained in step (2) in a reaction vessel, add benzocyclobutene-4-dimethylsilane and solvent under a nitrogen atmosphere, stir and mix evenly, then add catalyst, and then heat to 50-100℃ and react for 12-24h. After the reaction is completed, cool the reaction solution to 25℃, concentrate, purify and dry to obtain POSS modified monomer.

[0021] The method for preparing the POSS modified monomer of the present invention uses a vinyl POSS (T8-POSS) with a T8 structure as the basic skeleton, and introduces a hydrophobic perfluoroalkyl chain (SF) and a thermosensitive benzocyclobutenyl (Si-B) unit onto its inorganic cage through a thiol-ene click reaction and a hydrosilylation reaction.

[0022] In step (1), each reaction raw material is first taken. The reaction raw materials can be prepared using conventional methods known in the art, or can be purchased directly through commercial channels.

[0023] In step (2), the octavinyl cage-type silsesquioxane and 1H,1H,2H,2H-perfluorodecyl thiol undergo a thiol-ene click reaction under ultraviolet light irradiation in the presence of a photoinitiator. A hydrophobic perfluoroalkyl chain (SF) is introduced onto the inorganic cage of the octavinyl cage-type silsesquioxane, and the resulting intermediate is named T8V. x SFy, where x+y=8, x and y are both integers or decimals greater than 0, and the selection of x and y corresponds to the above-mentioned POSS modified monomer structural formula. In step (2), T8V with different values ​​of x and y can be prepared by changing the molar ratio of octavinyl cage-type silsesquioxane to 1H,1H,2H,2H-perfluorodecylthiol and controlling the irradiation time. x SFy. For example, when the molar ratio of octavinyl cage-type silsesquioxane to 1H,1H,2H,2H-perfluorodecylthiol is 1:1.8 and the irradiation time is 2-10 min, T8V can be obtained. 6.4 SF 1.6 .

[0024] Step (3) involves intermediate T8V x SFy is further reacted with benzocyclobutene-4-dimethylsilane in the presence of a catalyst, and through a hydrosilylation reaction, a thermosensitive benzocyclobutene (Si-B) unit is introduced onto the inorganic cage of the octavinyl cage-type silsesquioxane to prepare T8B. x SF y This refers to the POSS modified monomer described in this invention.

[0025] The benzocyclobutene-4-dimethylsilane in step (1) can be prepared using methods known in the art, or can be purchased directly. In this application, the benzocyclobutene-4-dimethylsilane is prepared using the following method:

[0026] Step S1: Add 4-bromobenzocyclobutene to anhydrous THF to prepare a homogeneous solution, then add it dropwise to a reaction vessel containing magnesium shavings and an initiator, heat to 40-70℃ and maintain the reaction for 0.5-10h, then cool the reaction system to 25℃.

[0027] Step S2: Add a solution of dimethylchlorosilane dissolved in anhydrous THF dropwise to the reaction vessel of step S1 while stirring. After the addition is complete, heat the reaction solution to 40-70℃ and react for 1-12 hours.

[0028] Step S3: After the reaction is complete, the mixture is quenched, concentrated, and purified to obtain a colorless and transparent liquid, which is benzocyclobutene-4-dimethylsilane.

[0029] In step S1, 4-bromobenzocyclobutene is first added to an appropriate amount of anhydrous THF to prepare a homogeneous solution, typically at 25°C. The mass content of 4-bromobenzocyclobutene in the prepared homogeneous solution can be, for example, 0.2 g / ml. Then, the prepared homogeneous solution is added dropwise to a reaction vessel containing magnesium shavings and a small amount of initiator, such as a three-necked flask. The mixture is then heated to 70°C and stirred for 1 hour. Subsequently, the reaction system is cooled to 25°C.

[0030] In step S2, the dimethylchlorosilane solution dissolved in anhydrous THF is prepared by dissolving dimethylchlorosilane in anhydrous THF. For example, the ratio of dimethylchlorosilane to anhydrous THF can be 0.27 mol: 50 ml. After the addition is complete, the reaction solution is heated to 70°C and reacted for 2 hours. After the reaction is complete, a colorless and transparent liquid, benzocyclobutene-4-dimethylsilane, is obtained through quenching, concentration, and purification.

[0031] Preferably, in step S1, the molar ratio of 4-bromobenzocyclobutene to magnesium shavings is 0.1:10 to 1:1.

[0032] The initiator in step S1 is iodine; the amount of initiator added is generally small.

[0033] The molar ratio of 4-bromobenzocyclobutene in step S1 to dimethylchlorosilane in step S2 is 0.1:1 to 2:1;

[0034] Preferably, dilute hydrochloric acid is used for quenching in step S3;

[0035] Preferably, the concentration process in step S3 is as follows: the organic phase is extracted with DCM, dried with anhydrous sodium sulfate, and then concentrated by rotary evaporation;

[0036] Preferably, column chromatography is used for purification in step S3. The eluent used in the column chromatography purification includes, but is not limited to, ethyl acetate and n-hexane in a volume ratio of 1:200 (EA:HEX = 1:200).

[0037] The organic solvent used in step (2) is preferably capable of dissolving octavinylcage-type silsesquioxane and providing a reaction system for its reaction with 1H,1H,2H,2H-perfluorodecylthiol. The organic solvent may include, but is not limited to, anhydrous DCM. The molar ratio of the octavinylcage-type silsesquioxane to the organic solvent may include, for example, 0.032 g: 1 ml.

[0038] The photoinitiator in step (2) can initiate the reaction between octavinylcage silsesquioxane and 1H,1H,2H,2H-perfluorodecylthiol under ultraviolet light irradiation. The photoinitiator may include, but is not limited to, 2,2-dimethoxy-2-phenylacetophenone. The amount of photoinitiator added may include, but is not limited to, a molar ratio of 1:20 between the photoinitiator and octavinylcage silsesquioxane. Stirring in step (2) is typically carried out at 25°C for, but is not limited to, 10 minutes.

[0039] In step (2), the ultraviolet light irradiation mainly provides suitable illumination conditions for octavinyl cage-type silsesquioxane and 1H,1H,2H,2H-perfluorodecyl mercaptan. The wavelength of the ultraviolet light is, for example, including but not limited to 254-580nm, preferably 365nm. The ultraviolet light can be a 365nm ultraviolet light (50W).

[0040] Preferably, the UV lamp irradiation reaction time in step (2) is 2-10 minutes; during the UV lamp irradiation reaction in step (2), through... 1 H NMR is used to track changes in the peak integral area of ​​vinyl hydrogen in T8V8 to detect the reaction process. The photoreaction usually lasts 2-10 minutes.

[0041] After the reaction in step (2) is completed, turn off the ultraviolet lamp and remove most of the organic solvent by rotary evaporator.

[0042] The purification method in step (2) is as follows: Excess cold methanol is added to the product after removing the organic solvent. The product is stirred until fully precipitated, and the solid product is collected by filtration and washed with a small amount of cold methanol. The product after removing the organic solvent is a viscous substance. Excess cold methanol is added to it, and the product is stirred until fully precipitated. The solid product is then collected by filtration and washed with a small amount of cold methanol, for example, 5 ml of cold methanol is used for washing three times each time for purification. The collected solid after purification is dried to obtain the intermediate. The drying process includes, but is not limited to, drying in a vacuum oven at 40°C for 24 hours.

[0043] In step (3), the intermediate is placed in a reaction vessel, such as, but not limited to, a 100 ml two-necked flask. Nitrogen gas is then purged three times. Benzocyclobutene-4-dimethylsilane and a solvent are added sequentially under a nitrogen atmosphere, and the mixture is stirred immediately. The molar ratio of the intermediate to benzocyclobutene-4-dimethylsilane is 0.1:1 to 1:10; the molar ratio of the intermediate to the solvent is, for example, but not limited to, 1.88 mmol:45 ml.

[0044] The solvent in step (3) is a liquid reaction system capable of providing a reaction system for the intermediate with benzocyclobutene-4-dimethylsilane, and the solvent includes, but is not limited to, anhydrous toluene.

[0045] In step (3), after the intermediate and benzocyclobutene-4-dimethylsilane are mixed and stirred evenly in the solvent, the catalyst is added. The amount of catalyst added is preferably, but not limited to, 188 mmol: 1 ml. The catalyst can be added by dripping with a microsyringe.

[0046] In step (3), the catalyst reacts with benzocyclobutene-4-dimethylsilane using a catalytic intermediate. The catalyst may be selected from, but is not limited to, Karstedt catalyst (2 wt.%, xylene solution). Karstedt catalyst is a highly efficient platinum-based catalyst whose chemical nature is a platinum(0)-vinylsiloxane complex. The Karstedt catalyst (2 wt.%, xylene solution) indicates that the mass fraction of the active ingredient (platinum) in the catalyst is 0.5-20 wt.%, that is, 0.5-20 g of platinum (calculated as metallic platinum) per 100 g of the solution, with the remainder being ligands and xylene solvent.

[0047] And / or, in step (3), the concentration is performed by rotary evaporation and the purification is performed by column chromatography. The eluent used in the column chromatography purification includes, but is not limited to, ethyl acetate and n-hexane in a volume ratio of 1:3 (EA:HEX = 1:3).

[0048] Thirdly, the present invention also provides a coating prepared using the POSS-modified monomer as described above. In the preparation process of the coating described in this invention, the POSS-modified monomer is generally prepared by thermosetting.

[0049] The methods for preparing the coating include, but are not limited to:

[0050] The POSS-modified monomer is dissolved in an organic solvent, such as DCM, to obtain a POSS-modified monomer solution. The mass percentage of POSS monomer in the POSS-modified monomer solution is 200 mg / mL. The POSS-modified monomer solution is then uniformly coated onto a substrate. The solvent is allowed to evaporate naturally under a nitrogen atmosphere at 25°C (the mass of the substrate coated with the POSS-modified monomer solution no longer decreases within 30 minutes). The sample is then placed under a pre-set heating program for thermosetting. The heating program includes, but is not limited to, 200°C / 0.5h, 230°C / 0.5h, and 260°C / 0.5h, with a heating rate of 5°C / min. -1 The corresponding C-T8B is obtained. x SF y coating.

[0051] The substrate is preferably, but not limited to, at least one of quartz sheets, glass substrates, metal plates, and organic CPI plates. When the substrate is selected from options other than a copper plate, the substrate needs to be treated with oxygen plasma before coating with the POSS modified monomer solution to enhance the adhesion between the coating and the substrate. Specifically, the substrate, which has been cleaned sequentially in deionized water, acetone, ethanol, and IPA, is treated with oxygen plasma for 2 minutes.

[0052] When the POSS modified monomers are T8B 6.4 SF 1.6 T8B 5.5 SF 2.5 T8B 5.1 SF 2.9 At that time, coatings C-T8B can be formed by thermosetting the coating onto the substrate. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 .

[0053] The present invention also provides a device comprising a substrate and a coating coated on the substrate, the coating containing the POSS modified monomer as described above.

[0054] Preferably, the substrate is at least one of a quartz sheet, a glass substrate, a metal plate, and an organic CPI plate.

[0055] More preferably, the glass substrate is a glass substrate containing ITO, and the metal plate is a copper plate.

[0056] The POSS-modified monomer of this invention has a vinyl POSS (T8-POSS) with a T8 structure, and a hydrophobic perfluoroalkyl chain (SF) and a thermosensitive benzocyclobutenyl (Si-B) unit are introduced into its inorganic cage. During use, the hybrid network structure can be constructed by adjusting the content of SF and Si-B units, thereby achieving the effect of controlling the optical, mechanical, thermal and surface wetting properties of the coating. When the POSS-modified monomer is used as a coating material in flexible devices, the coating not only has good mechanical properties, but also has excellent environmental barrier effects such as water and oxygen barrier and corrosion resistance, and can be widely used in flexible devices.

[0057] The POSS modified monomer of this invention has a basic framework of vinyl POSS (T8-POSS) with a T8 structure. Hydrophobic perfluoroalkyl chains (SF) and thermosensitive benzocyclobutenyl (Si-B) units are introduced into its inorganic cage. When it is thermocured to form a multifunctional coating, the hybrid network structure can be constructed by adjusting the content of SF and Si-B units, so as to achieve the effect of controlling the optical, mechanical, thermal and surface wetting properties of the coating, and has both high mechanical strength and environmental barrier efficiency.

[0058] The method for preparing the POSS modified monomer of the present invention uses a vinyl POSS (T8-POSS) with a T8 structure as the basic skeleton. Through a thiol-ene click reaction and a hydrosilanization reaction, a hydrophobic perfluoroalkyl chain (SF) and a thermosensitive benzocyclobutenyl (Si-B) unit are introduced onto its inorganic cage. The method has simple process steps, uses readily available raw materials, and can efficiently prepare the POSS modified monomer with the described structure.

[0059] The coating described in this invention is prepared using the POSS modified monomer. The coating has good mechanical properties and environmental barrier properties such as water and oxygen barrier and corrosion resistance, providing a new coating material option for flexible devices. Attached Figure Description

[0060] Figure 1 A schematic diagram of the synthesis reaction of benzocyclobutene-4-dimethylsilane in this invention.

[0061] Figure 2 This is a schematic diagram of the reaction process for preparing the POSS-modified monomer of the present invention.

[0062] Figure 3 T8V is the intermediate in the preparation process of the POSS modified monomer of the present invention. x SF y The nuclear magnetic resonance spectrum of [the image]. Figure 3 In the diagram, a represents the hydrogen spectrum, and b represents the fluorine spectrum.

[0063] Figure 4 The T8B prepared in Examples 1-3 of this invention6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The nuclear magnetic resonance spectrum of [the image]. Figure 4 In the spectrum, a represents the hydrogen spectrum and b represents the silicon spectrum.

[0064] Figure 5 The T8B prepared in Examples 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 Product photos.

[0065] Figure 6 The T8B prepared in Examples 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The DSC curve.

[0066] Figure 7 This is a schematic diagram of the crosslinking mechanism and crosslinking network for preparing the coating using the POSS-modified monomers of this invention; Figure 7 In Figure a, we see the crosslinking mechanism of the POSS-modified monomer; in Figure b, we see a schematic diagram of the crosslinking network formed by the POSS-modified monomer through thermosetting.

[0067] Figure 8 The T8B prepared in Examples 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 Infrared spectra, thermosetting time-resolved infrared spectra, and DSC curves of the prepared coating; Figure 8 In the middle, 'a' represents the T8B prepared in Examples 1-3. 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 b is the infrared spectrum of T8B prepared in Examples 1-3; 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9Thermosetting time-resolved infrared spectrum; c is the T8B prepared in Examples 1-3. 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The DSC curve.

[0068] Figure 9 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 XPS spectra, SEM-EDS images, and the ratio of F to Si elemental content at different depths; Figure 9 In the text, 'a' represents coating C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 XPS spectra; b represents coating C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 SEM-EDS image; c represents coating C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The ratio of F to Si content at different depths.

[0069] Figure 10 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 HRTEM (SAED, illustration) and EDS photographs.

[0070] Figure 11 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The ultraviolet-visible spectrum.

[0071] Figure 12 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The indentation test results are shown in the image. Figure 12 In the image, a is a schematic diagram of an indentation test performed on a sample using a nanoindenter equipped with a Berkovich-tipped nanoindenter; b is a C-T8B... 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Representative load-displacement curves; c represents C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 H and E * ; d represents the H / E ratio of various samples. * and We This includes metals such as Ni, Ti, and Cu, and organic polymers such as PP, PC, and PMMA.

[0072] Figure 13 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The results of the abrasion resistance test; Figure 13 In the image, a is a photograph of the steel wool abrasion test apparatus, and b is a photograph of the C-T8B test apparatus at ~10.0 kPa. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 SEM image of the coating after 500 friction cycles; c represents C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Ultraviolet transmittance (T) 500 nm ) is a function of the number of friction cycles; d is C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Surface AFM modulus diagram.

[0073] Figure 14 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Pencil hardness and C-T8B6.4 SF 1.6 Photos of flexibility and strength tests; Figure 14 In the text, 'a' represents coating C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The pencil hardness; b is the coating C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Photos of the flexibility and strength tests.

[0074] Figure 15 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The TGA curve.

[0075] Figure 16 The T8B described in Embodiments 1-3 of this invention 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The prepared coating C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Water absorption rate as a function of time, WCA, surface AFM phase diagram, and inferred surface structure; Figure 16 In the text, 'a' represents coating C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The water absorption rate is a function of time; b is C-T8B 6.4 SF 1.6 C-T8B5.5 SF 2.5 and C-T8B 5.1 SF 2.9 WCA; c is C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Surface AFM phase diagram; d represents C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The inferred surface structure.

[0076] Figure 17 In this context, 'a' represents the T8B described in Embodiment 1 of the present invention. 6.4 SF 1.6 The prepared coating C-T8B 6.4 SF 1.6 a) Adhesion strength with Cu glass and CPI substrates; b) OTR and WVTR properties of common polymers; c) Transition state structure of O2 and H2O insertion into T8-POSS; d) Interaction energy spectrum of O2 and H2O insertion into T8-POSS. Detailed Implementation

[0077] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0078] The sources of the raw materials used in the following examples are described in Table 1 below.

[0079] Table 1. Description of the sources of some raw materials used in the examples.

[0080] name purity Supplier 4-Bromobenzocyclobutene (BCB-Br) 99％ Shanghai Bid Pharmaceutical Technology Co., Ltd. Magnesium (Mg) 99％ Sinopharm Chemical Reagent Co., Ltd. Tetrahydrofuran (THF) 99％ Bailingwei Technology Co., Ltd. dimethylchlorosilane 96％ Shanghai Aladdin Chemical Reagent Co., Ltd. Dichloromethane (DCM) 96％ Shanghai Adamas Reagent Co., Ltd. Octadecyl-POSS (T8V8) 98％ Shanghai Myriel Chemical Technology Co., Ltd. 2,2-Dimethoxy-2-phenylethyl ketone (DMPA) 99％ Shanghai Inocare Technology Co., Ltd. Toluene (Tol) 99％ Sinopharm Chemical Reagent Co., Ltd. Karstedt catalyst, in xylene, Pt ~ 2% 98％ Shanghai Adamas Reagent Co., Ltd. Ethyl acetate (EA) 99％ Shanghai Adamas Reagent Co., Ltd. n-Hexane (HEX) 96％ Shanghai Adamas Reagent Co., Ltd. acetone ≥99％ Sinopharm Chemical Reagent Co., Ltd. Isopropyl alcohol (IPA) 98％ Shanghai Adamas Reagent Co., Ltd. Ethanol (EtOH) 98％ Shanghai Adamas Reagent Co., Ltd. <![CDATA[Chloroform-d (CDCl3)]]> 99％ Shanghai Adamas Reagent Co., Ltd. Perfluorooctyl ethanethiol (SF) 97％ Shanghai Adamas Reagent Co., Ltd.

[0081] The toluene is dehydrated before use: a small amount of CaH2 is added to the toluene, and after reflux for 12 hours, the fraction with a boiling range of 108-111℃ is collected by vacuum distillation.

[0082] The benzocyclobutene-4-dimethylsilicon (Si-B) used in the following examples was prepared in-house, and the specific preparation method includes the following steps:

[0083] Step S1: At 25°C, 4-bromobenzocyclobutene (BCB-Br, 50.00 g, 0.27 mol) was added to 250 ml of anhydrous THF to prepare a homogeneous solution. Then, it was added dropwise to a three-necked flask containing magnesium shavings (Mg, 7.95 g, 0.33 mol) and a small amount of iodine. The temperature was raised to 70°C and the reaction was stirred for 1 h. The reaction system was then cooled to 25°C.

[0084] Step S2: While stirring, add dropwise a solution of dimethylchlorosilane (25.85 g, 0.27 mol) dissolved in 50 mL of anhydrous THF to the three-necked flask of step S1. After the addition is complete, heat the reaction solution to 70 °C and react for 2 h.

[0085] Step S3: After the reaction was completed, the product was quenched with dilute hydrochloric acid (1M), the organic phase was extracted with DCM, dried with anhydrous sodium sulfate, and then concentrated by rotary evaporation. The crude product was purified by column chromatography. The eluent used in column chromatography was ethyl acetate and n-hexane at a volume ratio of 1:200 (EA:HEX = 1:200). After purification, a colorless and transparent liquid was obtained, which was benzocyclobutene-4-dimethylsilane (Si-B). The mass of benzocyclobutene-4-dimethylsilane obtained was 41.60 g, and the yield was 95.0%.

[0086] A schematic diagram of the reaction process for preparing benzocyclobutene-4-dimethylsilane is attached. Figure 1 As shown.

[0087] The 1H NMR and 13C NMR spectra of the obtained benzocyclobutene-4-dimethylsilicon (Si-B) are as follows:

[0088] 1 H NMR (400MHz, CDCl3, ppm): δ7.39(d,1H,ArH),7.24(s,1H,ArH),7.07(d,1H,ArH),4.41(m,1H,Si-H),3.16(s,4H,-CH2CH2-),0.31(d,6H,-CH3).

[0089] 13 C NMR (100MHz, CDCl3, ppm): δ147.12, 145.46, 135.03, 132.24, 127.47, 121.88, 29.22.

[0090] Unless otherwise specified, other raw materials can be obtained using conventional methods and known purchasing channels in the field.

[0091] The preparation method of the POSS-modified monomer of the present invention includes the following steps:

[0092] Step (1): Take benzocyclobutene-4-dimethylsilane, octavinyl cage-type silsesquioxane and 1H,1H,2H,2H-perfluorodecylthiol respectively;

[0093] Step (2): Under a nitrogen atmosphere, add octavinyl cage-type silsesquioxane to an organic solvent and stir to dissolve. Then add 1H,1H,2H,2H-perfluorodecylthiol and photoinitiator. After stirring evenly, irradiate the reaction with a UV lamp. After the reaction is complete, remove the organic solvent, purify and dry to obtain the intermediate.

[0094] Step (3): Place the intermediate obtained in step (2) in a reaction vessel, add benzocyclobutene-4-dimethylsilane and solvent under a nitrogen atmosphere, stir and mix evenly, then add catalyst, and then heat to 100℃ and react for 12h. After the reaction is completed, cool the reaction solution to 25℃, concentrate, purify and dry to obtain POSS modified monomer.

[0095] The reaction process diagram of the POSS-modified monomer is attached. Figure 2 As shown.

[0096] The following examples illustrate the methods for testing the structure and performance of POSS-modified monomers or coatings and devices prepared therefrom:

[0097] (1) Nuclear magnetic resonance spectroscopy 1 H NMR, 13 C NMR and 29 Si NMR)

[0098] NMR of all samples 1 H NMR, 13 C NMR and 29 Si NMR data were obtained on a Bruker 400 or 500 MHz (Bruker, AVANCE III HD 400) spectrometer at 298.15 K (25 °C). Chemical shifts (δ) are expressed in ppm. Deuterated chloroform (CDCl3) was used as the deuterating reagent, and tetramethylsilane (TMS) was used as the internal standard (CDCl3: 1 H-NMR δ 7.26ppm and 13 C-NMR δ 77.16 ppm; TMS: 1 H-NMR, 13 C-NMR and 29 Si-NMR (δ 0.00 ppm), 1 The H-NMR concentration was 10 mg·mL⁻¹. -1 , 13 C-NMR and 29 The Si-NMR concentration was 20 mg·mL⁻¹. -1.

[0099] (2) Atomic force microscope (AFM)

[0100] All coatings and samples were characterized for nanostructure and mechanical properties using atomic force microscopy (AFM) at 298.15 K (25 °C) on an Oxford MFP-3D (UK-Oxford Instruments). Modulus, phase, and height diagrams were obtained for each sample. Samples were attached to clean glass slides, purged with nitrogen (N2) to remove dust, and then wiped with anhydrous ethanol (EtOH). Testing was conducted after the ethanol evaporated.

[0101] (3) Pencil hardness

[0102] All pencil hardness tests were conducted using an Elecometer 501 pencil hardness tester, in accordance with ASTM D3363. Pencils ranging from softest to hardest, including 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, and 9H, were purchased from Mitsubishi Corporation. During the test, the pencil was held at a 45° angle against the coated surface and then pushed forward. Pencil hardness was determined based on the hardest pencil that could withstand the test without causing damage to at least three distinct areas of the coating.

[0103] (4) Differential Scanning Calorimeter (DSC)

[0104] DSC tests on all samples were performed on a Discovery DSC 800 (TA Instruments, USA). Samples were tested under a N2 atmosphere at 10°C for [time missing]. -1 The heating and cooling rates were tested within a temperature range of 50-300℃.

[0105] (5) Fourier transform infrared spectroscopy (FTIR)

[0106] The sample was coated onto a potassium bromide plate, and then infrared spectra were measured using a Nicolet iS50 in-situ infrared spectrometer (Thermofisher, USA) in Fourier transform transmission mode, with a wavenumber range of 4000-400 cm⁻¹. -1 .

[0107] (6) Thermogravimetric analysis (TGA)

[0108] The thermal degradation properties of all samples were tested using a Discovery TGA550 (TA Instruments, USA). All tests were conducted under an N2 atmosphere with a flow rate of 40 mL / min. -1 Then at 20℃ min -1The temperature was increased from room temperature (25℃) to 120℃ and held at this temperature for 10 min to remove residual moisture from the sample. It was then lowered to 40℃ and again increased at 10℃ min. -1 The heating rate increased to 800℃.

[0109] (7) Nanoindentation

[0110] Using an Agilent G200 nanoindenter (CSMI Instruments, Switzerland) equipped with a 15 μm diameter diamond Berkovich tip, at room temperature and 0.005 s... -1 Nanoindentation tests were performed on the coating at a constant strain rate. To avoid substrate interference, all samples were 100 μm thick, and the penetration depth of the indenter was less than 10% of the coating thickness. The load range was 0-40 mN / m. -1 The loading / unloading rate is 5 mN / s. -1 The Oliver-Pharr method was used to calculate the hardness (H) and effective Young's modulus (E). * ) and elastic recovery rate (W e ).

[0111] (8) Optical performance

[0112] The UV-Vis transmittance of the films and coatings was analyzed using a UV-1800 spectrophotometer (Shimadzu Corporation, Japan), with a wavelength acquisition range of 200-800 nm. The color gradation of the polyimide films was analyzed using a Lambda 950 UV-Vis-NIR analyzer (PerkinElmer Corporation, USA).

[0113] (9) Scratch resistance

[0114] The scratch test was conducted on a steel wool abrasion resistance testing apparatus. Steel wool (#0000 grade, 25μm width) was wrapped around the end of an HSR-2M type scratch resistance tester (Changzhou Ruipin Precision Instruments Co., Ltd., China) and secured with steel wire. The coating was adhered to a glass substrate, and the abrasion resistance test was conducted under an average vertical pressure of approximately 13.0 kPa. One complete friction cycle was recorded as one friction cycle.

[0115] (10) Transmission electron microscope-energy dispersive X-ray spectroscopy (TEM-EDS)

[0116] TEM and selected area electron diffraction (SEAD) images of the samples were acquired using a JEM-2100F microscope (JEOL Ltd., Japan) at an accelerating voltage of 200 kV. After grinding, the samples were ultrasonically separated in ethanol, then removed and transferred to a copper grid for further characterization. The elemental distribution of the sample surface was characterized using an energy-dispersive X-ray spectroscopy probe on the TEM. All samples underwent thin-layer gold sputtering before observation. The contrast of the sample images was enhanced using a bandpass filter in ImageJ (version 1.54g).

[0117] (11) Scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS)

[0118] The surface morphology of the samples was analyzed using RISE-MAGNA (Czech-TESCAN), and the elemental distribution of the sample surface was characterized using an energy-dispersive X-ray spectroscopy probe on RISE-MAGNA. All samples underwent thin-layer gold sputtering before observation. The contrast of the sample images was enhanced using a bandpass filter in ImageJ (version 1.54g).

[0119] (12) Surface energy

[0120] Contact angles were measured at room temperature using a DSA100 contact angle measuring instrument (KRUSS GmbH, Germany), with a volume of 5 μL for each droplet (water and diiodomethane). Surface energy for all samples was calculated using the Owens-Wendt-Rabel-Kaelble (WORK) method.

[0121] (13) Theoretical Calculation

[0122] Density functional theory (DFT) calculations were performed using Gaussian 16 software and the B3LYP functional def2TZVP basis set.

[0123] (14) X-ray photoelectron spectroscopy (XPS)

[0124] The elemental composition and content of the sample surface were determined using a GENESIS 900 X-ray photoelectron spectrometer (ULVAC Fiennes, Japan).

[0125] (15) Water vapor transmission rate (WVTR)

[0126] The water vapor transmission rate (WVTR) of all samples was measured using a W3-062 water vapor transmission rate testing system (China-Jinan Langguang Electromechanical Technology Co., Ltd.). Samples used for OTR measurement were also subjected to WVTR testing here, under the following conditions: 23°C and 50% RH on the permeation side, and 5% RH on the dry side. The coated side of the film faced the dry side.

[0127] (16) Oxygen Transmission Rate (OTR)

[0128] The oxygen permeability (OTR) of all samples was evaluated using a C203H oxygen permeability testing system (China-Jinan Langguang Electromechanical Technology Co., Ltd.). Measurements were performed according to the ASTM D-3985 standard method at 25±2°C and 50%±1 relative humidity (RH). The results are the average of at least three repeated measurements.

[0129] (17) Water absorption rate

[0130] The water absorption rate of all samples was calculated using the differential method. First, the film samples were dried in a vacuum drying oven at 80℃ for 24 hours, then naturally cooled to room temperature, and the initial mass m0 was recorded. Subsequently, the same sample was immersed in deionized water, and the mass m of the samples immersed for different times was measured. n The water absorption rate of the film is calculated based on the following formula:

[0131]

[0132] (18) Oxygen Plasma

[0133] After purging the surface of the thin film or coating with nitrogen, it is attached to the glass and then placed in a DT-01 low-temperature plasma treatment instrument (China-Suzhou Aopus Plasma Technology Co., Ltd.). The cavity atmosphere is replaced with O2, and then etched at 150W for 5 minutes.

[0134] (19) Adhesion

[0135] The interlaminar strength of the samples was tested using a Romulus IV pull-out tester (Quad Group, Japan).

[0136] Example 1

[0137] One embodiment of the POSS-modified monomer of the present invention, wherein the POSS-modified monomer described in this embodiment is named T8B. 6.4 SF 1.6 Its preparation method includes the following steps:

[0138] Step (1): Take benzocyclobutene-4-dimethylsilane (3.05 g, 18.8 mmol), octavinyl cage-type silsesquioxane (0.64 g, 1.00 mmol) and 1H,1H,2H,2H-perfluorodecyl mercaptan (SF, 0.87 g, 1.80 mmol) respectively;

[0139] Step (2): Under a nitrogen atmosphere, octavinylclade silsesquioxane was added to a 100 mL three-necked flask containing 20 mL of anhydrous DCM and stirred to dissolve. Then, 1H,1H,2H,2H-perfluorodecylthiol SF and photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA, 11.14 mg, 0.05 mmol) were added. After stirring at 25 °C for 10 min, the reaction was irradiated with a 365 nm UV lamp (50 W). 1 ¹H NMR was used to monitor the reaction progress by tracking the change in the peak integral area of ​​vinyl hydrogen in T8V8. The photoreaction usually lasts 2-10 min. After the reaction, the UV lamp was turned off, and most of the DCM was removed by rotary evaporation. Then, excess cold methanol (30 mL) was added to the resulting viscous residue, and the product was allowed to precipitate completely with stirring. The waxy solid product was collected by vacuum filtration and washed with a small amount of cold methanol (3 × 5 mL). The collected waxy solid was dried in a vacuum oven at 40 °C for 24 h to obtain product T8V8. 6.4 SF 1.6 (1.34g, yield 95.6%) is the intermediate;

[0140] Step (3): The intermediate obtained in step (2) (2.63 g, 1.88 mmol) was placed in a dry 100 mL two-necked flask, and then nitrogen gas was purged three times. Under a nitrogen atmosphere, benzocyclobutene-4-dimethylsilicon Si-B (3.05 g, 18.8 mmol) and 45 mL of anhydrous toluene were added to the reaction flask in sequence, and the mixture was stirred immediately. After the reaction mixture was homogeneous, 0.01 mL of Karstedt catalyst (2 wt.%, xylene solution) was added dropwise through a microsyringe. The reaction system was then slowly heated to 80 °C and reacted for 12 h. After the reaction was completed, the reaction solution was cooled to 25 °C and concentrated by rotary evaporation. The crude product was purified by column chromatography (EA:HEX = 1:3). After concentration and drying, the final waxy solid T8B was obtained. 6.4 SF 1.6 (1.669g, yield 36.4%) is the POSS modified monomer of this embodiment.

[0141] Example 2

[0142] One embodiment of the POSS-modified monomer of the present invention, wherein the POSS-modified monomer described in this embodiment is named T8B. 5.5 SF 2.5The preparation method of the POSS modified monomer described in this embodiment differs from that in Example 1 only in that: the amount of SF in step (1) is adjusted to 1.22g, the amount of Si-B in step (1) is adjusted to 2.45g, the reaction system is slowly heated to 70℃ for 5h, and the ultraviolet lamp in step (1) is replaced with a 254nm (50W) irradiation lamp.

[0143] Example 3

[0144] One embodiment of the POSS-modified monomer of the present invention, wherein the POSS-modified monomer described in this embodiment is named T8B. 5.1 SF 2.9 The preparation method of the POSS modified monomer described in this embodiment differs from that in Example 1 only in that: the amount of SF in step (1) is adjusted to 1.45g, the amount of Si-B in step (1) is adjusted to 2.06g, the reaction system is slowly heated to 100℃ and reacted for 5h, and the ultraviolet lamp in step (1) is replaced with a 254nm (100W) irradiation lamp.

[0145] Example 4

[0146] Structural characterization of the POSS-modified monomer of the present invention

[0147] The POSS-modified monomer T8B of this invention x SF y The octavinyl cage-type silsesquioxane T8V8 was prepared by introducing functional substituents SF and Si-B onto the thiol-olefin click chemistry reaction and subsequent hydrosilylation reaction, respectively. Where x and y are respectively introduced via... 1 The area ratio of the hydrogen proton signal peaks of SF and Si-B obtained by H NMR, with x+y=8. The longer SF carbon-fluorine chain provides excellent hydrophobicity, but it has high repulsion with POSS. Photogenerated radical-mediated thiol-alkene reactions can efficiently and regioselectively construct carbon-sulfur (CS) single bonds. This process usually follows the anti-Markovnikov addition rule, thus ensuring the structural regularity of the product. For T8V8 with terminal alkenes, this is an ideal strategy for attaching fluorinated segments to the POSS cage.

[0148] To explore the optimal combination of hydrophobicity, mechanical properties, and stability, this example prepared T8V with different molar amounts of SF. x SF y And the T8V obtained with different SF molar amounts... x SF y The proton and fluorine NMR spectra were performed, and the results are attached. Figure 3 As shown.

[0149] From the appendix Figure 3 As shown in a and b, with the increase of SF molar amount, the area of ​​the hydrogen characteristic peak (5.75-6.25 ppm) of vinyl groups in T8V8 gradually decreases, while the area of ​​the hydrogen on the methylene group (2.25-3.30 ppm) in SF gradually increases. Meanwhile, all T8V... x SF y Fluorine atom signal peaks of SF were observed in the fluorine spectra of all samples, indicating that SF was precisely introduced into the POSS cage.

[0150] On the other hand, Si-B units were also introduced onto the POSS cage via a hydrosilylation reaction. Si-B was chosen as another functional substituent because its benzocyclobutene unit can be thermally activated to form the active intermediate o-quinodimethane. Under thermal action, this intermediate can further self-polymerize to form dimers or polymers without producing any small molecule byproducts, resulting in a resin with advantages such as high thermal stability, mechanical properties, and low water absorption. To ensure T8V... x SF y The remaining vinyl groups were entirely replaced by Si-B, therefore an excess of Si-B was added. T8V was used for different SF molar amounts. x SF y T8B with different x and y values ​​were prepared respectively. x SF y The proton and silicon nuclear magnetic resonance spectra were also performed, and the results are attached. Figure 4 As shown.

[0151] From the appendix Figure 4 As can be seen from 'a' and 'b', it belongs to T8V. x SF y The peak of the vinyl group completely disappeared, while the characteristic peak of the hydrogen atom of the benzene ring in Si-B appeared in the range of 7.01-7.40 ppm, and the characteristic peak of the hydrogen atom of the four-membered ring in Si-B appeared at 3.16 ppm. Based on the ratio of the characteristic peak area of ​​the hydrogen atom on the methylene group in SF to that of the hydrogen atom in the four-membered ring in Si-B, the SF:Si-B ratios can be obtained as 6.4:1.6, 5.5:2.5, and 5.1:2.9, thus determining the prepared T8B. x SF y The chemical formula is T8V 6.4 SF 1.6 T8V 5.5 SF 2.5 and T8V 5.1 SF 2.9Furthermore, all T8BxSFy silicon spectra exhibited two silicon atom signal peaks at -0.67 ppm and -66.41 ppm. The former is attributed to silicon atoms in Si-B, while the latter is a silicon atom signal peak in the cage-like POSS framework of the T8 structure. Figure 4 (b) This demonstrates that introducing functional substituents SF and Si-B onto the POSS cage of T8V8 via thiol-olefin and hydrosilylation reactions does not disrupt the configuration of the Si-O-Si framework and cage.

[0152] Example 5

[0153] Physical morphology of the POSS-modified monomer of the present invention

[0154] The physical morphologies of the starting material, octavinyl cage-type silsesquioxane T8V8, and the product after chemical modification to introduce long-chain SF groups and Si-B groups were observed respectively. The results are attached. Figure 5 As shown.

[0155] From the appendix Figure 5 It can be seen that the aggregation states of these series of products exhibit significant differences: the starting material T8V8 is a solid powder, while the physical morphology of the products undergoes a significant change after chemical modification to introduce long-chain SF groups and Si-B groups. Specifically, T8B... 6.4 SF 1.6 It appears as a hard, waxy solid, T8B 5.5 SF 2.5 It is a soft, waxy solid, while T8B 5.1 SF 2.9 It then transforms into a viscous liquid. This transformation from a solid to a waxy and liquid state is because SF and Si-B disrupt the interactions between POSS cages, and the high content of long carbon fluorine chains makes it easier to interfere with the orderly stacking of molecular chains.

[0156] Example 6

[0157] Thermal performance test of the POSS modified monomer of the present invention

[0158] T8B was revealed by differential scanning calorimetry (DSC). x SF y The thermal properties of the series of compounds are presented in the form of heat flow-temperature curves, and the results are attached. Figure 6 As shown.

[0159] From the appendix Figure 6 It can be seen that T8B has a waxy appearance. 6.4 SF 1.6 and T8B 5.5 SF 2.5 All exhibited a clear endothermic melting peak (T) during the heating process.m The melting points of these compounds are 59.6 °C and 70.9 °C, respectively. Furthermore, these compounds containing Si-B groups exhibit similar exothermic curing behavior at higher temperatures: their exothermic reaction initiation temperature (T0) is [not specified]. onset The temperature range is between 197.3 and 200.3℃, while the peak exothermic temperature (T) is... peak The temperature range is 244.4-248.8℃. This exothermic behavior originates from the formation of highly reactive o-quinodimethane intermediates from the highly strained four-membered rings in the Si-B groups at high temperatures. These intermediates then couple with each other to form a highly cross-linked, dense network structure, releasing a large amount of heat. T8B, with the highest Si-B group content... 6.4 SF 1.6 It exhibits the largest exothermic enthalpy of the curing reaction, at 300.2 kJ / mol, T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The exothermic enthalpies are 255.3 kJ / mol and 243.5 kJ / mol, respectively, and their exothermic enthalpy ratio is approximately 6.4:5.5:5.1, which is similar to T8V. 6.4 SF 1.6 T8V 5.5 SF 2.5 and T8V 5.1 SF 2.9 The stoichiometric trends of the Si-B groups in the middle are basically consistent.

[0160] Example 7

[0161] Thermosetting performance test of the POSS modified monomer described in this invention

[0162] Take the POSS-modified monomer T8B prepared in Examples 1-3 respectively 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 The coating is prepared using the following method as a raw material:

[0163] Quartz plates, which had been sequentially cleaned in deionized water, acetone, ethanol, and IPA, were treated with oxygen plasma for 2 minutes. Then, T8B dissolved in DCM was... 6.4 SF 1.6 Solution (200 mg / mL), T8B dissolved in DCM 5.5 SF 2.5 Solution (200 mg / mL), T8B dissolved in DCM 5.1 SF 2.9The solution (200 mg / mL) was evenly coated onto the quartz plates.

[0164] The solvent was allowed to evaporate naturally under a nitrogen atmosphere at 25°C (within 30 minutes after coating with T8B). 6.4 SF 1.6 (The mass of the quartz sheet no longer decreases), and then the sample is placed in a pre-set heating program for heat curing: 200℃ / 0.5h, 230℃ / 0.5h, and 260℃ / 0.5h, with a heating rate of 5℃ / min. -1 The corresponding coatings were obtained, namely C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 .

[0165] The crosslinking mechanism of the POSS modified monomer and a schematic diagram of the crosslinked network coating formed by thermosetting are shown in the attached figure. Figure 7 As shown.

[0166] POSS-modified monomer T8B was tested separately. 6.4 SF 1.6 T8B 5.5 SF 2.5 and T8B 5.1 SF 2.9 Infrared spectrum, T8B 6.4 SF 1.6 Thermosetting time-resolved infrared spectra and the obtained coatings C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The DSC curves are shown in the attached figure. Figure 8 As shown.

[0167] C-T8B x SF y The coating is achieved through thermosetting T8B. x SF y The thermal crosslinking process, which is prepared by monitoring T8B, can be achieved through this process. x SF y The changes in the four-membered ring of benzocyclobutene are thus revealed. (See attached image.) Figure 8 As shown in a, b, and c, the FITR spectrum reveals T8B x SF y All of them contain stretching vibration peaks (1115 cm⁻¹) belonging to the Si-O-Si cage framework of the POSS. –1 The stretching vibration peak of the fluoroalkyl chain CF (1247 cm⁻¹)–1 And the characteristic peak of benzocyclobutene (930 cm⁻¹) –1 and 1465cm –1 The heating process at 1465 cm⁻¹ was monitored using time-resolved infrared spectroscopy (TR-FTIR). –1 The changes in peak values ​​are used to develop specific curing procedures. (T8B) 6.4 SF 1.6 Taking thermal crosslinking as an example, when it is heated from 30℃ to 280℃, the characteristic peak of benzocyclobutene completely disappears at ~260℃, indicating that T8B 6.4 SF 1.6 Complete cross-linking has been achieved. Figure 8 (b) C-T8B x SF y The DSC curve did not show an exothermic peak, thus confirming the reliability of thermosetting. Figure 8 (c)

[0168] Example 8

[0169] The coating C-T8B prepared in Example 7 was tested separately. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 XPS spectra, SEM-EDS images, and the ratio of F to Si elemental content at different depths are shown in the attached figures. Figure 9 As shown.

[0170] X-ray photoelectron spectroscopy (XPS) revealed the chemical composition of the three coating surfaces in the ~10 nm range. For example... Figure 9 As shown in Figure a, O was clearly observed on all coated surfaces. KLL (978.4eV)F KLL (833.6eV), F 1s (688.8eV), O 1s (532.0eV), C 1s (284.0eV)Si 2s (152.8eV) and Si 2p Characteristic peaks such as (101.6 eV) confirm that they have the same elemental composition. The C-T8B composition can be calculated by analyzing the areas of the characteristic peaks of each element and combining them with the corresponding atomic sensitivity factors. x SF y The F / Si elemental ratio on the surface of the series of coatings is significantly higher than its theoretical (bulk) stoichiometric ratio. Figure 9 (b) Figure 8The scanning electron microscope (SEM) image in c shows that C-T8B x SF y No macroscopic phase separation was observed on the surface of the series of coatings, but C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The surface smoothness decreases sequentially. The corresponding energy-dispersive X-ray spectroscopy (EDS) shows a uniform distribution of Si, S, F, O, and C elements within 1–3 μm of their surfaces. Figure 9 c, illustration), but the F / Si elemental ratio is higher than in the bulk, but lower than that measured by XPS ( Figure 9 b). These results strongly suggest that SF segments with low surface energy tend to migrate to the coating-air interface and achieve enrichment there through specific orientation.

[0171] Example 9

[0172] To further explore C-T8B x SF y The microstructure and elemental distribution characteristics of the series of coatings at the nanoscale are analyzed in this example. The coating C-T8B prepared in Example 7 is analyzed separately. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 High-resolution transmission electron microscopy (HRTEM) and its accompanying energy-dispersive X-ray spectroscopy (EDS) were performed, and the results are attached. Figure 10 As shown.

[0173] From the appendix Figure 10 It can be seen that C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The HRTEM images all showed uniform contrast, with no lattice fringes or obvious domain structures observed, indicating that the bulk of these organic-inorganic hybrid materials is amorphous. This is strongly confirmed by their selected area electron diffraction (SAED) patterns. Figure 10(Illustration). SAED patterns of all samples exhibit typical diffuse diffraction rings, rather than discrete diffraction spots representing a crystal structure. This amorphous structure is crucial for achieving high optical transparency, as it effectively avoids light scattering caused by grain boundaries. Combined EDX elemental surface scan results further reveal the spatial distribution of key elements at the nanoscale. It can be clearly observed that fluorine (F) (purple) and sulfur (S) (yellow), representing fluoroalkyl segments, highly overlap in spatial distribution, confirming their common origin from SF functional groups. Furthermore, silicon (Si) (cyan), representing the POSS inorganic core, exhibits a uniform and dense distribution throughout the entire observation area of ​​all samples. These results collectively indicate that C-T8B... x SF y The series of coatings successfully formed a highly uniform, molecular-level organic-inorganic hybrid network structure, without any macroscopic or microscopic agglomeration caused by component incompatibility.

[0174] Example 10

[0175] C-T8B obtained by preparing POSS-modified monomers according to the present invention x SF y Optical performance test of coating

[0176] The coating C-T8B formed on the quartz substrate in Example 7. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 Ultraviolet-visible spectroscopy was performed, and the results are attached. Figure 11 As shown.

[0177] From the appendix Figure 11 It can be seen that, across the entire visible light range (400-800nm), all C-T8B... x SF y All coatings exhibited excellent high transparency. However, detailed comparison revealed a clear negative correlation between the optical transmittance of the coating and the SF content in its chemical composition. Specifically, as the SF segment content increased, the overall transmittance of the coating gradually decreased, as seen in C-T8B. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The coating at 550nm (T 550 nmThe transmittances of the three components were 94.7%, 92.6%, and 91.4%, respectively. The slight decrease in transmittance may stem from two factors. First, with the increase in the proportion of the high-refractive-index SF component, the refractive index of the coating decreased from 1.41 (C-T8B). 6.4 SF 1.6 Systematically increase by 1.48 (C-T8B) 5.5 SF 2.5 ) and 1.51(C-T8B 5.1 SF 2.9 According to Fresnel's law, the greater the difference in refractive index between the coating and air (n≈1.0), the stronger the light reflection from its surface, leading to a corresponding decrease in total transmittance. Secondly, higher SF content results in increased surface roughness and more significant micro-phase separation, leading to increased light scattering at these inhomogeneous interfaces. Nevertheless, even the C-T8B with the weakest optical performance... 5.1 SF 2.9 The coating's transmittance remains comparable to that of commercially available cover materials (CPI < 90.0%), indicating that C-T8B... x SF y All coatings in this series can meet the application requirements for high transparency.

[0178] High optical transmittance of the protective coating within the device's operating wavelength range is crucial, as it directly determines the number of photons that can effectively enter or exit the device, thus profoundly affecting the overall efficiency and performance of the device. For example, in organic light-emitting diode (OLED) displays, high transmittance ensures that light generated by the emissive layer can pass through the cover glass with minimal loss, ultimately resulting in higher brightness and better energy efficiency. Typically, light absorption and scattering within a material are the two main factors affecting its transparency. C-T8B x SF y The series of coatings exhibit weak absorption in the visible light region. Meanwhile, their molecular-level organic-inorganic hybrid network and the amorphous morphology formed after curing can theoretically effectively suppress light scattering caused by inhomogeneous structures, thus possessing the potential to prepare highly transparent coatings.

[0179] Example 11

[0180] C-T8B obtained by preparing POSS-modified monomers according to the present invention x SF y Mechanical property testing of coating

[0181] The coating C-T8B formed on the quartz substrate in Example 7. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1SF 2.9 Nanoindentation experiments were conducted, and the results are attached. Figure 12 As shown in Table 2.

[0182] In this embodiment, a series of nanoindentation experiments were conducted based on the Oliver-Pharr method. The Berkovich indenter was used to load the samples, and the load-displacement curve for each sample included three typical stages: loading, holding, and unloading (see attached diagram). Figure 12 (a and b) Under the same indentation depth, C-T8B 6.4 SF 1.6 The coating requires the highest load, indicating its highest hardness. Furthermore, after the load is released, C-T8B... 6.4 SF 1.6 The coating exhibits the least hysteresis in its load-displacement curve, indicating that it also has the best resilience. Figure 12 C-T8B was obtained through nanoindentation testing. x SF y Indentation hardness (H) and effective Young's modulus (E) of the series coatings * In these coatings, C-T8B 6.4 SF 1.6 The coating exhibits the highest hardness (H = 0.17 GPa) and a modulus (E) similar to that of high-performance polymers. * =2.90 GPa).

[0183] In addition, Table 2 summarizes the C-T8B obtained through calculation. x SF y Elastic recovery rate (W) of the series coatings e ) and hardness / effective Young's modulus ratio (H / E) * Two key parameters. W e The hysteresis loop area in the load-displacement curve characterizes the material's ability to recover elastic deformation after load removal. A smaller hysteresis loop area indicates better elastic recovery performance. (H / E) * The W value is often used to evaluate a material's resistance to plastic deformation: when a material has sufficient hardness to resist indentation, a lower effective modulus helps reduce material stiffness, giving it better flexibility. Therefore, a higher W value... e With H / E * This usually indicates that the material can better balance hardness, flexibility, and elastic recovery properties.

[0184] With C-T8B x SF y H and E series coatings * The trend of change is the same for C-T8B 6.4 SF 1.6 W coating e and H / E* The values ​​remain the highest. These coatings were compared with common engineering materials, including organic polymers (PC, PMMA, and PP) and metals (Ni, Ti, and Cu). Figure 12 (d). Obviously, C-T8B 6.4 SF 1.6 The coating exhibits significant advantages, suggesting that it may balance the inherent contradiction between hardness and flexibility.

[0185] Table 2 Mechanical properties determined by nanoindentation testing

[0186] <![CDATA[Samples a) ]]> H(GPa) <![CDATA[E * (GPa)]]> <![CDATA[W e (%)]]> <![CDATA[H / E * (%)]]> <![CDATA[C-T8B 6.4 SF 1.6 ]]> 0.17 2.90 70.18 5.86 <![CDATA[C-T8B 5.5 SF 2.5 ]]> 0.15 2.71 67.62 5.55 <![CDATA[C-T8B 5.1 SF 2.9 ]]> 0.12 2.33 54.21 5.22

[0187] Note: The data in Table 2 are the average of three measurements.

[0188] An ideal protective coating for transparent optoelectronic devices should simultaneously possess the high hardness of glass (to resist scratches and abrasion), the excellent flexibility of polymers (to accommodate deformation and impact), high resilience (to recover from deformation), and a relatively low elastic modulus (to be compatible with flexible substrates and reduce stress), thereby ensuring stable device operation under various operating conditions. The above results show that the C-T8B prepared from the POSS-modified monomer of this invention… x SF y The coating has good overall mechanical properties.

[0189] Example 12

[0190] C-T8B obtained by preparing POSS-modified monomers according to the present invention x SF y Abrasion resistance test of coating

[0191] As one of the service characteristics of a coating, wear resistance is directly related to the service life, performance stability, and safety of the protected object. This example compares the C-T8B coating prepared in Example 7. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 A steel wool abrasion test (10.0 kPa) was conducted to examine the wear resistance characteristics of each coating. The test results are attached. Figure 13 As shown.

[0192] like Figure 13 As shown in Figure b, after 500 friction cycles (1000 cycles), C-T8B 5.1 SF 2.9 The coating surface is covered with numerous clearly visible scratches, C-T8B 5.5 SF 2.5A small number of wear marks were also observed on the coating surface. Surprisingly, C-T8B 6.4 SF 1.6 The coating surface showed almost no damage under the same wear conditions, and its ultraviolet light transmittance was not affected by friction. Figure 13 (b and c). In contrast, after continuous wear, C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 White debris caused by friction appeared on the coating surface, resulting in a significant decrease in its ultraviolet light transmittance. Figure 13 (c) These phenomena strongly confirm C-T8B. 6.4 SF 1.6 The coating exhibits superior wear resistance. Generally, there is a positive correlation between the hardness of a material and its wear resistance, and in some cases, this can manifest as a strong linear relationship, as observed in C-T8B. 6.4 SF 1.6 The high hardness is consistent with the result of high wear resistance.

[0193] Figure 13 The middle section shows the C-T8B. x SF y AFM modulus maps of a series of coatings are presented, visually reflecting the nanoscale elastic modulus distribution on the material surface through color variations. Although no large-scale, significant modulus abrupt changes or discontinuous regions are observed in the modulus distribution of each coating, the surface modulus of the material decreases with increasing SF content, evolving from a dense, broadly high-modulus region to a coarse-grained, inhomogeneous modulus domain.

[0194] Theoretically, a uniform and dense modulus distribution network is beneficial for achieving more uniform internal stress dispersion under external forces. This structural characteristic allows the material to maintain high surface hardness while also possessing excellent toughness. The coating C-T8B prepared in Example 7 was compared with this. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The pen's hardness and flexibility were tested, and the results are attached. Figure 14 As shown.

[0195] From the appendix Figure 14 It can be seen that only C-T8B 6.4 SF 1.6 The coating can withstand the scratches of a 9H pencil without damage, compared to a C-T8B of the same thickness. 5.5 SF 2.5 and C-T8B5.1 SF 2.9 The pencil hardness of the coating is only 7H and 5H respectively. Figure 14 (a)

[0196] In addition, C-T8B 6.4 SF 1.6 When applied to CPI, it can be bent into various complex shapes and will not break even when lifted with a 500g weight, demonstrating its excellent flexibility and mechanical strength. Figure 14 (b) These experimental results also demonstrate that C-T8B 6.4 SF 1.6 The optimal ratio of soft to hard components and the appropriate crosslinking density combine to create a coating that possesses the high hardness of glass, the excellent flexibility of polymers, and outstanding elastic recovery, making it a potential protective coating for flexible transparent devices.

[0197] Example 13

[0198] C-T8B obtained by preparing POSS-modified monomers according to the present invention x SF y Thermal performance test of coating

[0199] In this embodiment, thermogravimetric analysis (TGA) was used to analyze C-T8B. x SF y The thermal decomposition behavior of the series of coatings under a nitrogen atmosphere was characterized, with the C-T8B coating prepared in Example 7 being the test subject. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The test results are attached. Figure 15 As shown in Table 3 below.

[0200] Table 3. C-T8B obtained from the preparation of the POSS-modified monomer of the present invention. x SF y Thermal properties of the series coatings

[0201] <![CDATA[Samples a) ]]> <![CDATA[C-T8B 6.4 SF 1.6 ]]> <![CDATA[C-T8B 5.5 SF 2.5 ]]> <![CDATA[C-T8B 5.1 SF 2.9 ]]> <![CDATA[T d5 %(℃)]]> 466.8 433.3 408.6 <![CDATA[T d10 %(℃)]]> 523.2 479.6 443.7

[0202] Note a) Measurement under nitrogen atmosphere; T d5 % and T d10 The percentages represent the temperatures at which 5% and 10% of the mass is lost in heat, respectively.

[0203] From the appendix Figure 15 As shown in Table 3, when the SF content increases, the relative proportions of high-temperature resistant inorganic components and rigid aromatic ring structures in the entire system decrease, leading to a reduction in the residual mass after high-temperature decomposition. (C-T8B)6.4 SF 1.6 Coating heat loss 5% (T d5 %) and 10% (T) d10 The highest temperatures were reached at (%) mass, at 466.8℃ and 523.2℃, respectively. Although C-T8B had the highest SF content... 5.1 SF 2.9 It has the lowest thermal stability, but its T d5 The thermal stability remains as high as 408.6℃. This level of thermal stability is not only comparable to high-performance colorless polyimide (CPI) materials, but also fully meets the heat resistance requirements of foldable covers in practical applications. Because the cover differs from substrates or active layers that require high-temperature processes, its service environment typically does not involve such extreme high temperatures. Therefore, the C-T8B prepared in this study can be considered... x SF y All coatings in the series possess the thermal stability required for use as flexible display cover plates.

[0204] Furthermore, through detailed comparison of TGA spectra of coatings with different components, we found that the thermal stability of the coating is closely related to the content of fluoroalkyl chains (SF) in its chemical composition. With the increase of SF segment content, the final residue content of the coating at high temperatures gradually decreases. This phenomenon is reasonable because SF segments are mainly non-crosslinked organic components, and their thermal stability is lower than that of the inorganic Si-O-Si cage-like core and the rigid Si-B structure formed after crosslinking.

[0205] Example 14

[0206] C-T8B obtained by preparing POSS-modified monomers according to the present invention x SF y Water and oxygen barrier properties of the coating

[0207] Optoelectronic materials, such as solar cells (OSCs), organic light-emitting diodes (OLEDs), or optical sensors, are extremely sensitive to moisture. Water absorption can lead to a rapid decline in material performance or even complete failure. Coatings with water-barrier properties are crucial for maintaining the long-term stable and reliable operation of optoelectronic devices.

[0208] To evaluate the C-T8B obtained from the preparation of the POSS-modified monomer of this invention x SF y The water-blocking performance of the coating is demonstrated in this example using the C-T8B coating prepared in Example 7. 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9The membrane, used as the experimental subject, was immersed in water along with a CPI membrane used as a reference, and the water absorption rate was continuously monitored at different time points. The results are attached. Figure 16 As shown.

[0209] From the appendix Figure 16 As can be seen from Figure a, the water absorption rate of all samples increases with the extension of soaking time. However, the difference lies in the saturated water absorption rate of the CPI membrane, which is C-T8B. x SF y More than ten times that of a series of coatings. The difference in hydrophobicity of the material surfaces is a significant reason for this phenomenon (e.g., Figure 16 b): C-T8B x SF y The series of coatings exhibits excellent hydrophobicity, with a water contact angle (WCA) between 104.5° and 106.5°, significantly higher than the 89.0° of the CPI film. This makes it difficult for water droplets to spread and wet their surface. Additionally, C-T8B... x SF y The highly dense three-dimensional cross-linked network inside the series of coatings can reduce the free volume, thereby hindering the diffusion and penetration of water molecules in the material bulk, and thus further reducing the water absorption rate.

[0210] Interestingly, despite C-T8B 6.4 SF 1.6 C-T8B 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The coatings contained varying amounts of SF segments, but their hydrophobicity and water absorption (both <0.2%) showed no significant differences. AFM surface phase diagrams revealed that this difference was likely due to the different microstructures formed by the SF enriched on the coating surface. Figure 16 In the middle c, it can be clearly observed that C-T8B has the lowest SF content. 6.4 SF 1.6 The coating surface exhibits the smallest phase separation scale; in contrast, with increasing SF content, C-T8B... 5.5 SF 2.5 and C-T8B 5.1 SF 2.9 The phase separation scale on the coating surface shows a gradually increasing trend. Combined with XPS and EDS elemental distribution data and AFM modulus plots, we can reasonably infer the specific arrangement of SF segments on different coating surfaces. Figure 16 (d) C-T8B 6.4 SF 1.6 The small number of SF chains in the coating may preferentially adopt an alternating dispersed arrangement, while in C-T8B 5.5 SF 2.5 and C-T8B5.1 SF 2.9 In the coating, the numerous SF segments are more likely to self-aggregate on the surface, forming larger-scale SF-rich domain regions. These different surface nanostructures can effectively construct a highly efficient hydrophobic barrier on the outermost layer of the coating, thus endowing the material with excellent overall water-blocking properties.

[0211] Considering that excessive SF chains can damage C-T8B x SF y The series of coatings does not significantly improve the mechanical properties (hardness and abrasion resistance), thermal properties, or optical properties of the coating, nor does it significantly improve the hydrophobic properties of the coating. Therefore, C-T8B... 6.4 SF 1.6 The coating is considered the most suitable candidate for multi-functionality. It exhibits excellent adhesion to a variety of substrates, including metallic copper (Cu), as well as inorganic glass and organic polymer CPI substrates pretreated with O2 plasma.

[0212] The POSS-modified monomers prepared in Example 1 were coated onto Cu glass and CPI substrates according to the method in Example 7. The interfacial bonding strength and water-oxygen barrier effect of the POSS-modified monomers coated on different substrates were investigated. Simultaneously, the T8-H8 cage (with eight silicon vertices replaced by hydrogen atoms) was used as a molecular insertion model to study the effects of O2 and H2O on the geometry of the T8-POSS cage. The results are attached. Figure 17 As shown.

[0213] From the appendix Figure 17 As can be seen from a, C-T8B 6.4 SF 1.6 A very strong interfacial bond was formed between the coating and the O2 plasma-treated CPI substrate, with an adhesion strength as high as 11 MPa. Analysis suggests that although O2 plasma treatment introduces a large number of oxygen-containing polar groups (e.g., -OH) onto the substrate surface (such as CPI), these groups can interact with C-T8B... 6.4 SF 1.6 The Si-O-Si framework in the coating forms hydrogen bonds, which improves interfacial adhesion to some extent, but this is not the decisive factor in achieving such high bonding strength. AFM morphology images show that the CPI film surface treated with O2 plasma exhibits a significantly rough, porous structure at the nanoscale. We infer that T8B... 6.4 SF 1.6 The solution penetrates and fills these pores and depressions, and then solidifies in situ during subsequent heat treatment, forming a strong interlock with the CPI substrate, known as the "riveting effect." This physical anchoring is what makes C-T8B so special. 6.4 SF 1.6 The coating is the primary source of the excellent interfacial bonding strength between the coating and the treated CPI substrate.

[0214] The water and oxygen barrier effect of coating the POSS-modified monomer prepared in Example 1 onto the CPI substrate according to the method in Example 7 is shown in the attached figure. Figure 17 As shown in b, by Figure 17 As can be seen in b, compared to the uncoated bare CPI substrate, the C-T8B coated substrate... 6.4 SF 1.6 The CPI sample exhibited significantly improved water and oxygen barrier properties. Specifically, its water vapor transmission rate (WVTR) increased from 8 g / m² of the bare CPI. -2 day -1 Significantly reduced to 0.25gm -2 day -1 At the same time, the oxygen permeability (OTR) also increased from 230 cm⁻¹ 3 m -2 day - 1 atm -1 Significantly reduced to 0.6cm 3 m -2 day -1 atm -1 On the one hand, the dense organic cross-linked network formed by the thermosetting of Si-B groups can hinder gas permeation, while the hydrophobic SF alkyl chains enhance the repulsion of water molecules. On the other hand, C-T8B with a D4 symmetry plane... 6.4 SF 1.6 The inorganic cage of the coating cannot become a channel for the permeation of O2 and H2O molecules, which can be proven by density functional theory (DFT).

[0215] Meanwhile, in this embodiment, a T8H8 cage (where the eight vertices of silicon are replaced by hydrogen atoms) was selected as the molecular insertion model to study the effects of O2 and H2O on the geometry of the T8-POSS cage, as shown in the attached figure. Figure 17 As shown in Figure c, this figure shows that, for the O2 molecule, it causes the Si(1)-O(1) bond distance to increase from that in isolated POSS. Increase to To increase the size of the cage; since the OH bond is weaker than the O=O bond, H2O makes the increase in Si-O bond distance in isolated POSS slightly lower than that of O2, for In addition, O2 increases the Si(1)-O(1)-Si(1') bond angle of the T8-POSS cage from 147.62° to 150.90°, while H2O increases it to an even greater 152.54°. This is because O2 and H2O have different polarities, resulting in different interactions with the POSS cage, indicating that their entry would cause significant distortion of the cage's geometry. However, the T8-POSS cage has a stable geometry, making this situation highly unlikely.

[0216] Additionally, as attached Figure 17 As shown in Figure d, this embodiment investigated the energy distribution when O2 and H2O were partially inserted into the D4 face of the T8-POSS cage. The energy barrier for O2 partial insertion was higher than that for H2O, which is related to their insertion angle, but the energy barriers that needed to be overcome were both >10.00 kcal / mol. -1 This indicates that they would encounter significant resistance when entering the POSS cage.

[0217] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A POSS-modified monomer, characterized in that, Its structural formula is shown below: In the structural formula: R is vinyl; x+y=8, where x and y are both integers or decimals greater than 0; The SF group is the following:

2. The POSS-modified monomer as described in claim 1, characterized in that, The condition is 1≤x<8, and y is 0-8.

3. A method for preparing a POSS-modified monomer as described in claim 1, characterized in that, The preparation method includes the following steps: Step (1): Take benzocyclobutene-4-dimethylsilane, octavinyl cage-type silsesquioxane and 1H,1H,2H,2H-perfluorodecylthiol respectively; Step (2): Under a nitrogen atmosphere, add octavinyl cage-type silsesquioxane to an organic solvent and stir to dissolve. Then add 1H,1H,2H,2H-perfluorodecylthiol and photoinitiator. After stirring evenly, irradiate the reaction with a UV lamp. After the reaction is complete, remove the organic solvent, purify and dry to obtain the intermediate. Step (3): Place the intermediate obtained in step (2) in a reaction vessel, add benzocyclobutene-4-dimethylsilane and solvent under a nitrogen atmosphere, stir and mix evenly, add catalyst, and then heat to 50-100℃ for 5-24h. After the reaction is completed, cool the reaction solution to 25℃, concentrate, purify and dry to obtain POSS modified monomer.

4. The method for preparing the POSS-modified monomer as described in claim 3, characterized in that, The benzocyclobutene-4-dimethylsilane in step (1) is prepared by the following method: Step S1: Add 4-bromobenzocyclobutene to anhydrous THF to prepare a homogeneous solution, then add it dropwise to a reaction vessel containing magnesium shavings and an initiator, heat to 40-70℃ and maintain the reaction for 0.5-10h, then cool the reaction system to 25℃. Step S2: Add a solution of dimethylchlorosilane dissolved in anhydrous THF dropwise to the reaction vessel of step S1 while stirring. After the addition is complete, heat the reaction solution to 40-70℃ and react for 1-12 hours. Step S3: After the reaction is complete, the mixture is quenched, concentrated, and purified to obtain a colorless and transparent liquid, which is benzocyclobutene-4-dimethylsilane.

5. The method for preparing the POSS-modified monomer as described in claim 4, characterized in that, In step S1, the molar ratio of 4-bromobenzocyclobutene to magnesium shavings is 0.1:10 to 1:

1. And / or, the initiator in step S1 is iodine; And / or, the molar ratio of 4-bromobenzocyclobutene in step S1 to dimethylchlorosilane in step S2 is 0.1:1 to 2:1; And / or, in step S3, dilute hydrochloric acid is used for quenching; And / or, the concentration process in step S3 is as follows: the organic phase is extracted with DCM, dried with anhydrous sodium sulfate, and then concentrated by rotary evaporation; And / or, in step S3, column chromatography is used for purification.

6. The method for preparing the POSS-modified monomer as described in claim 3, characterized in that, The organic solvent in step (2) is anhydrous DCM; And / or, the photoinitiator in step (2) is 2,2-dimethoxy-2-phenylacetophenone; And / or, the wavelength of the ultraviolet light irradiation in step (2) is 254-580nm; And / or, the time for the ultraviolet light irradiation reaction in step (2) is 2-10 min; And / or, after the reaction in step (2) is completed, the organic solvent is removed by a rotary evaporator; And / or, the purification process in step (2) is as follows: add excess cold methanol to the product after removing the organic solvent, allow the product to precipitate fully under stirring, collect the solid product by filtration, and wash with a small amount of cold methanol.

7. The method for preparing the POSS-modified monomer as described in claim 3, characterized in that, In step (3), the molar ratio of the intermediate to benzocyclobutene-4-dimethylsilane is 0.1:1 to 1:10; And / or, the solvent in step (3) is anhydrous toluene; And / or, the catalyst in step (3) is a Karstedt catalyst (0.5-20 wt.%, xylene solution); And / or, in step (3), rotary evaporation is used for concentration and column chromatography is used for purification.

8. A coating, characterized in that, The coating is prepared using the POSS-modified monomer as described in any one of claims 1-2.

9. A device, characterized in that, The device includes a substrate and a coating applied to the substrate, the coating containing a POSS-modified monomer as described in any one of claims 1-2.

10. The application of the POSS-modified monomer as described in claim 1 or 2 in flexible devices.

Images