A chemical-resistant glass based on a nanocomposite coating and its application

Abstract

This invention discloses a chemical-resistant glass based on a nanocomposite coating and its applications, belonging to the field of glass technology. The chemical-resistant glass based on the nanocomposite coating includes surface-treated glass and a nanocomposite coating applied to its upper and lower surfaces. The nanocomposite coating, by weight, comprises the following components: 30-35 parts epoxy resin, 25-35 parts modified phenolic resin, 3-5 parts nano-pigments and fillers, 25-30 parts inactive diluent, 5-15 parts reactive diluent, and 0.5-1.5 parts additives. The modified phenolic resin is obtained by modifying phenolic resin with a benzo[a]heterocyclic cyano modifier. This invention, through a combination of molecular structure design, nanocomposite technology, and process optimization, successfully prepares a nanocomposite coating and glass products with good adhesion, high hardness, excellent transparency, and chemical corrosion resistance, exhibiting superior comprehensive performance and practical application value.

Description

Technical Field

[0001] This invention belongs to the field of glass technology, specifically relating to a chemical-resistant glass based on a nanocomposite coating and its applications. Background Technology

[0002] With the development of modern industry, the requirements for glass performance in fields such as chemical corrosion protection, medical devices, semiconductor manufacturing, and precision analytical instruments are becoming increasingly stringent. Glass components must simultaneously meet the core requirements of good transparency, mechanical strength, and long-term resistance to corrosive media such as strong acids, strong alkalis, and organic solvents. Ordinary glass or glass with simple surface treatments can no longer meet the needs of extreme working conditions.

[0003] Surface functional coatings are an efficient and economical means to improve the chemical resistance of glass. Among them, epoxy-phenolic resin systems have become the mainstream research direction due to their excellent adhesion, rigidity and chemical resistance. However, existing nanocomposite chemical-resistant glass coating technologies still face multiple challenges: First, there is a bottleneck in chemical resistance. Traditional epoxy-phenolic curing networks are easily swollen and destroyed when exposed to strong solvents or extreme pH environments for extended periods, leaving little room for molecular structure optimization. Second, the dispersion stability of nanoparticles and fillers is poor. Due to their large specific surface area and high surface energy, nanoparticles easily agglomerate in the resin matrix, forming secondary aggregates. This not only fails to exert a reinforcing effect but also becomes stress concentration points, reducing the coating's density. Third, there is a contradiction between coating internal stress and transparency. While high-temperature rapid curing can increase crosslinking density, it easily induces internal stress, leading to microcracks or decreased adhesion. Furthermore, nanoagglomeration and curing volume shrinkage scatter visible light, affecting applications in the optical field. Fourth, the process controllability and reproducibility are poor. The nanodispersion, coating formulation, and curing processes lack precise quantitative parameters, making it difficult to translate laboratory results into industrial applications, resulting in large batch-to-batch variations and low yield rates.

[0004] In summary, current technology urgently needs a novel solution that can significantly improve the intrinsic chemical resistance of coatings while overcoming the technical challenges of nano-pigment and filler dispersion stability and coating internal stress control, and achieve precise and controllable process, thereby producing chemical-resistant glass products with good overall performance and stable reliability. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, this invention provides a chemical-resistant glass based on a nanocomposite coating. Through a combination of molecular structure design, nanocomposite technology, and process optimization, a nanocomposite coating and glass product with good adhesion, high hardness, excellent transparency, and chemical corrosion resistance were successfully prepared. The technical solution to achieve the objective of this invention is as follows:

[0006] A chemical-resistant glass based on a nanocomposite coating comprises surface-treated glass and nanocomposite coatings applied to its upper and lower surfaces; the nanocomposite coating, by weight, comprises the following components: 30-35 parts epoxy resin, 25-35 parts modified phenolic resin, 3-5 parts nano-pigments and fillers, 25-30 parts inactive diluent, 5-15 parts reactive diluent, and 0.5-1.5 parts additives; the modified phenolic resin is obtained by modifying phenolic resin with a benzo[a]heterocyclic cyano modifier; the benzo[a]heterocyclic cyano modifier includes one or more of benzo[a]oxazole cyano modifier and benzo[a]thiazole cyano modifier; the structure of the benzo[a]oxazole cyano modifier is shown in Formula 1, and the structure of the benzo[a]thiazole cyano modifier is shown in Formula 2.

[0007] Equation 1; Equation 2; where R in Equations 1 and 2 is a carbon chain with double bonds.

[0008] The epoxy resin is selected from one or two of bisphenol A type epoxy resin and bisphenol F type epoxy resin.

[0009] The nano pigments and fillers are selected from one or more of nano silica, nano zirconium oxide, nano titanium oxide, nano alumina, and nano montmorillonite.

[0010] The inactive diluent is selected from one or more of propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, cyclohexanone, and xylene.

[0011] The active diluent is selected from one or more of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and ethylene glycol diglycidyl ether.

[0012] The additive is selected from one or more of the following: polyether-modified polysiloxane, non-silicone defoamer, and polymeric dispersant.

[0013] The method for preparing the modified phenolic resin includes the following steps:

[0014] Phenolic resin was mixed with solvent and heated and stirred until the resin was completely dissolved. The system was cooled to ≤50℃ and vacuum dehydrated until no bubbles were generated. Then the temperature was raised to 90~100℃. The benzo[a]heterocyclic cyano modifier was dissolved in solvent and placed in a constant pressure dropping funnel for later use. 0.2% of triphenylphosphine relative to the mass of the modifier was added directly to the phenolic resin solution and stirred to disperse it evenly. The benzo[a]heterocyclic cyano modifier solution was slowly added dropwise through the constant pressure dropping funnel. After the addition was completed, the reaction was refluxed and the reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the mixture was cooled to ≤30℃, and the modified phenolic resin was discharged and stored in a sealed container.

[0015] The molar ratio of the phenolic resin to the benzene heterocyclic cyano modifier is 1:(0.95~1.05).

[0016] The solvent is selected from one or more of propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, cyclohexanone, and xylene.

[0017] The preparation method of the benzo[a]heterocyclic cyano modifier includes the following steps:

[0018] (1) Synthesis of benzo[a]heterocyclic cyanoalkenyl compounds: An anhydrous toluene solution of 2-benzoxazole acetonitrile was prepared in a dry flask. Acetic acid, ammonium acetate and enal were added to the solution. The reaction mixture was then heated to reflux. After the reaction was completed, the benzo[a]heterocyclic cyanoalkenyl compounds were purified.

[0019] (2) Synthesis of benzo[a]heterocyclic cyano modifier: Benzo[a]heterocyclic cyanoolefin compound, (S)-6,6'-bis(9-anthrayl)spirocyclodiol phosphate and magnesium sulfate were mixed, freshly distilled toluene was added, and hydrogen peroxide aqueous solution was added dropwise. The reaction was stirred and the reaction progress was detected by thin-layer chromatography. After the reaction was completed, the benzo[a]heterocyclic cyano modifier was obtained by purification.

[0020] The enal is selected from one or more of 6-nonenal, 5-octenal, 4-heptenal, 3-hexenal, and 3-pentenal.

[0021] A method for preparing chemical-resistant glass based on a nanocomposite coating includes the following steps:

[0022] S1. Preparation of two-component coating: Pour a portion of the non-reactive diluent and the reactive diluent into the dispersion tank of a high-speed stirred sand mill disperser. Connect the cooling water to the dispersion tank and slowly add bisphenol A type epoxy resin while stirring slowly. Then increase the speed of the high-speed stirred sand mill disperser and keep the temperature ≤50℃ to prepare a completely dissolved bisphenol A type epoxy resin solution, thus obtaining coating component A. Add modified phenolic resin, additives, and the remaining non-reactive diluent to a new dispersion tank and stir evenly. Slowly add nano pigment and filler powder in batches, increase the speed, and then add grinding beads to grind and disperse. Use centrifugal sedimentation to remove undispersed large agglomerates. Take the upper uniform slurry for use to obtain coating component B. Filter coating component A with a filter screen and mix it with coating component B, which has been centrifuged, in proportion. Degas under high vacuum, let stand, and then pour it into a spray gun for later use.

[0023] S2. Coating Application and Curing: The glass substrate is ultrasonically cleaned, dried with nitrogen, and then immersed in an ethanol-water solution of an epoxy silane coupling agent. After removal, it is cured and then kept at a constant temperature. In a clean environment, the coating is sprayed onto the treated glass surface from both above and below, keeping the spray gun at a consistent distance from the glass surface to obtain a coating with uniform thickness. After spraying, the glass substrate is transferred to an oven for gradient curing to obtain chemical-resistant glass based on the composite coating.

[0024] The zirconium oxide grinding beads have a particle size of 0.4~0.6 mm.

[0025] The gradient curing method involves holding the temperature at 75-85℃ for 50-70 min, then raising the temperature to 110-130℃ at a rate of 1-2℃ / min and holding for 50-70 min, then raising the temperature to 145-155℃ at the same rate and holding for 100-120 min, and finally holding at 155-165℃ for 100-120 min.

[0026] Another objective of this invention is to provide applications of the chemical-resistant glass based on the nanocomposite coating prepared by the above-described method for preparing chemical-resistant glass based on nanocomposite coating in the fields of industrial chemical engineering, medical and biotechnology, and household and daily consumer goods.

[0027] Beneficial effects

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. Excellent chemical resistance: This invention chemically modifies phenolic resin using a benzo[a]heterocyclic cyano modifier, introducing highly stable and rigid benzo[a]oxazole or benzo[a]thiazole ring structures and highly polar cyano groups into the phenolic resin skeleton. This modified phenolic resin, used as a curing agent, forms a three-dimensional cross-linked network with epoxy resin after curing, exhibiting extremely high cross-linking density and chemical inertness. This network resists the erosion of chemical media such as acids, alkalis, and organic solvents, demonstrating better chemical resistance than ordinary epoxy-phenolic coatings.

[0030] 2. Excellent adhesion and mechanical strength: On the one hand, the gradient temperature curing process used in the coating ensures slow solvent evaporation, full resin leveling, and gradual cross-linking, greatly reducing the internal stress of the coating and avoiding problems such as cracking and warping caused by rapid curing. On the other hand, the nano-pigments and fillers, under the efficient dispersion of the grinding beads, can be uniformly and stably dispersed in the resin matrix at the nanoscale, producing a significant nano-reinforcing effect, thereby endowing the coating with extremely high hardness, wear resistance, scratch resistance, and toughness.

[0031] 3. Long-lasting stability and high transparency: The nano-dispersion process employed in this invention effectively prevents the agglomeration and sedimentation of nano-pigments and fillers, ensuring the stability of the coating components during storage and solving common problems such as sedimentation and performance degradation in nanocomposite materials. Simultaneously, the optimized formulation and process enable the coating to maintain excellent transparency while possessing high strength, without affecting the light transmittance of the glass substrate, meeting the needs of high-end applications such as displays and optics.

[0032] 4. Wide range of applications: This chemical-resistant glass is not only suitable for corrosion protection in traditional chemical industries, but its high performance, high transparency and biocompatibility also make it a promising candidate for applications in medical analytical instruments, biochips, high-end laboratory equipment, semiconductor displays and other industries.

[0033] In summary, this invention, through a combination of molecular structure design, nanocomposite technology, and process optimization, successfully prepared a nanocomposite coating and glass products with good adhesion, high hardness, excellent transparency, and chemical corrosion resistance. These products exhibit superior overall performance and have practical application value. Attached Figure Description

[0034] Figure 1 The synthetic route for benzoxazole cyano modifier 1 is as follows.

[0035] Figure 2 The image shows the 1H NMR spectrum of benzoxazole cyanoalkenyl compound 1.

[0036] Figure 3 The image shows the 1H NMR spectrum of benzoxazole cyano modifier 1.

[0037] Figure 4 The image shows the infrared spectrum of modified phenolic resin 1. Detailed Implementation

[0038] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0039] Unless otherwise specified, the experimental methods used in the preparation examples and embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0040] The raw materials and equipment used in the preparation examples, embodiments, and comparative examples are described below, where eq represents molar equivalents:

[0041] Preparation Example

[0042] Preparation Example 1

[0043] Benzo[a]oxazole cyano modifier 1: self-made, preparation method as follows:

[0044] (1) Synthesis of benzoxazole cyanoalkenyl compound 1: An anhydrous toluene solution containing 1 eq of 2-benzoxazole acetonitrile with a concentration of 0.2 mol / L was prepared in a dry flask. 0.1 eq of acetic acid, 2 eq of ammonium acetate and 1 eq of 6-nonenal were added to the solution. The reaction mixture was then heated to reflux and the reaction progress was detected by thin-layer chromatography. After the reaction was completed, the flask was cooled to room temperature, the reaction mixture was washed with deionized water and extracted three times with ethyl acetate, the organic phases were combined, dried with anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the benzoxazole cyanoalkenyl compound 1 was obtained by silica gel column chromatography.

[0045] (2) Synthesis of benzoxazole cyano modifier 1: 1 eq of the above-mentioned benzoxazole cyano alkenyl compound 1, 0.3 eq of (S)-6,6'-bis(9-anthrayl)spirocyclodiol phosphate, and 10 eq of magnesium sulfate were mixed, 5 mL of freshly distilled toluene was added, and then 2.0 eq of 30% hydrogen peroxide aqueous solution was added dropwise. The reaction was stirred at 35°C, and the reaction progress was detected by thin-layer chromatography. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain benzoxazole cyano modifier 1 with an epoxy equivalent of 296 g / eq. The structure is shown in the following formula:

[0046] .

[0047] Preparation Example 2

[0048] Benzothiazole cyano modifier 2: self-made, the difference from benzoxazole cyano modifier 1 is that 2-benzoxazole acetonitrile is replaced with 2-benzothiazole acetonitrile, and all other conditions remain unchanged, to obtain benzothiazole cyano modifier 2 with an epoxy equivalent of 312 g / eq, and the structure is shown in the following formula:

[0049] .

[0050] Preparation Example 3

[0051] Benzoxazole cyano modifier 3: self-made, the difference between benzoxazole cyano modifier 1 and benzoxazole cyano modifier 3 is that 6-nonenal is replaced with 3-pentenal, and all other conditions remain the same. The resulting benzoxazole cyano modifier 3 has an epoxy equivalent of 240 g / eq, and its structure is shown in the following formula:

[0052] .

[0053] Preparation Example 4

[0054] Modifier 4: 1,2-epoxyoctane, commercially available.

[0055] Epoxy resin: Bisphenol A type epoxy resin, epoxy equivalent of 100~150 g / eq, commercially available.

[0056] Nano silica: purity ≥99.8%, particle size 30~50 nm, commercially available.

[0057] Additive: Polyether-modified polysiloxane, viscosity: 500~3000, commercially available.

[0058] Non-reactive diluent: Propylene glycol methyl ether acetate, commercially available.

[0059] Phenolic resin: hydroxyl equivalent of 100~150 g / eq, number average molecular weight of 500~1000, purchased from Jinan Shengquan Group Co., Ltd.

[0060] Example

[0061] Example 1

[0062] Modified phenolic resin 1: self-made, preparation method is as follows:

[0063] One eq of phenolic resin was mixed with propylene glycol methyl ether acetate and heated to 70°C. The mixture was mechanically stirred until the resin was completely dissolved. The system was cooled to ≤50°C, and dehydrated under a vacuum of -0.08 MPa until no bubbles were generated. The temperature was then raised to 95°C. One eq of benzoxazole cyano modifier 1 was dissolved in propylene glycol methyl ether acetate and placed in a constant-pressure dropping funnel. 0.2% (by mass) of triphenylphosphine was directly added to the phenolic resin solution at 95°C. The mixture was stirred to ensure uniform dispersion. The benzoxazole cyano modifier 1 solution was slowly added dropwise over 2 hours using a constant-pressure dropping funnel. After the addition was complete, the mixture was refluxed at 95°C, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to below 30°C and discharged to obtain modified phenolic resin 1. The hydroxyl equivalent of the obtained modified phenolic resin 1 was determined to be 118 g / eq, and the number-average molecular weight Mn = 923. g / mol (GPC, THF phase, polystyrene calibration), store in a sealed container.

[0064] Example 2

[0065] Modified phenolic resin 2: prepared in-house. The preparation method is the same as that of modified phenolic resin 1, except that benzoxazole cyano modifier 1 is replaced with benzothiazole cyano modifier 2, while other conditions remain unchanged. Modified phenolic resin 2 is obtained. The hydroxyl equivalent of the obtained modified phenolic resin 2 is 122 g / eq, and the number average molecular weight Mn = 942 g / mol. It is stored in a sealed container.

[0066] Example 3

[0067] Modified phenolic resin 3: prepared in-house. The preparation method is the same as that of modified phenolic resin 1, except that benzoxazole cyano modifier 1 is replaced with benzoxazole cyano modifier 3, while other conditions remain unchanged. Modified phenolic resin 3 is obtained. The hydroxyl equivalent of the obtained modified phenolic resin 3 is 115 g / eq, and the number average molecular weight Mn is 884 g / mol. It is stored in a sealed container.

[0068] Comparative Example 1

[0069] Modified phenolic resin 4: prepared in-house. The preparation method is the same as that of modified phenolic resin 1, except that benzoxazole cyano modifier 1 is replaced with modifier 4, while other conditions remain unchanged. Modified phenolic resin 4 is obtained. The hydroxyl equivalent of the obtained modified phenolic resin 4 is 125 g / eq, and the number average molecular weight Mn = 862 g / mol. It is stored in a sealed container.

[0070] Comparative Example 2

[0071] Phenolic resin 5: Phenolic resin with a hydroxyl equivalent of 100~150 g / eq and a number average molecular weight of 500~1500, commercially available.

[0072] Application examples

[0073] Application Examples 1-3

[0074] Chemical-resistant glass based on composite coating 1-3: self-made, preparation method is as follows:

[0075] S1. Preparation of two-component coating: Pour 10-15 parts of inactive diluent and 5-15 parts of reactive diluent into the dispersion tank of a high-speed stirred sand mill disperser. Connect condensate water to the dispersion tank. Slowly add 30-35 parts of bisphenol A epoxy resin at 400-600 rpm. Then set the speed of the high-speed stirred sand mill disperser to 2500 rpm and stir for 60 min, keeping the temperature ≤50℃, to prepare a completely dissolved bisphenol A epoxy resin solution, obtaining component A of the coating, and seal it in a package. Add 25-35 parts of modified phenolic resin, 0.5-1.5 parts of additives, and the remaining inactive diluent to a new dispersion tank. Set the speed of the high-speed stirred sand mill disperser to 2000 rpm and stir for 15 min to make it uniform. While stirring, slowly add 3-5 parts of nano-silica in batches to prevent agglomeration. After adding the materials, increase the speed to 2500 rpm and continue dispersing for 30 minutes. After 50-70% of the effective volume of the dispersion tank, zirconia grinding beads with a particle size of 0.4-0.6 mm are added. The speed is adjusted to 4000 rpm, and the mixture is circulated and milled for 90 minutes. The outlet slurry temperature is ≤45℃. The beads are collected by sieving at 300-500 rpm. Then, the undispersed large agglomerates are removed by centrifugal sedimentation at 10000 rpm for 30 minutes, while controlling the temperature to ≤35℃. The upper uniform slurry is used to obtain coating component B, which is sealed and packaged. Coating component A is filtered through a 200-mesh filter and mixed with the centrifuged coating component B in proportion. The mixture is degassed under vacuum of ≥-0.095 MPa for 5 minutes, allowed to stand for 30 minutes, and then poured into a spray gun for later use.

[0076] S2. Coating Application and Curing: The glass substrate is ultrasonically cleaned with acetone and ethanol, dried with nitrogen, and then immersed in a 1% solution of epoxy silane coupling agent in a 95:5 volume ratio of ethanol to water for 2 minutes. After removal, it is cured at 80℃ for 5 minutes, then heated to 120℃ and held for 5 minutes. In a clean environment, the coating is sprayed onto the treated glass surface. The air compressor is turned on, and the air pressure is adjusted to 0.55~0.6 MPa. The coating is applied in four up-and-down passes, with each pass producing approximately 0.5 mL / s. The overall atomization fan width is controlled at 1~1.5 revolutions. The spray gun is maintained at a 20 cm distance from the glass surface throughout the spraying process. The nozzle diameter is 1.0 mm, and the atomization pressure is 0.23~0.27. MPa, each wet film 40~45μm, three wet sprayings, each flash-drying for 5min, final dry film 35~45μm, avoiding thick coating and sagging in one go; after spraying, the glass substrate is transferred to an oven and held at 80℃ for 60min, then heated to 120℃ at a rate of 1~2℃ / min and held for 60min, then heated to 150℃ at the same rate and held for 120min, and finally heated to 160℃ at the same rate and held for 120min, to obtain chemical-resistant glass 1~3 based on composite coating.

[0077] Application Example 4

[0078] Chemical-resistant glass 4 based on composite coating: self-made, the preparation method is the same as that of chemical-resistant glass 1 based on composite coating, except that modified phenolic resin 1 is replaced with modified phenolic resin 2, and other conditions remain unchanged, thus obtaining chemical-resistant glass 4 based on composite coating.

[0079] Application Example 5

[0080] Chemical-resistant glass 5 based on composite coating: self-made. The preparation method is the same as that of chemical-resistant glass 1 based on composite coating, except that modified phenolic resin 1 is replaced with modified phenolic resin 3, while other conditions remain unchanged, thus obtaining chemical-resistant glass 5 based on composite coating.

[0081] Comparative Application Example 1

[0082] Chemical-resistant glass 6 based on composite coating: self-made, the preparation method is the same as that of chemical-resistant glass 1 based on composite coating, except that modified phenolic resin 1 is replaced with modified phenolic resin 4, and other conditions remain unchanged, thus obtaining chemical-resistant glass 6 based on composite coating.

[0083] Comparative Application Example 2

[0084] Chemical-resistant glass 7 based on composite coating: self-made. The preparation method is the same as that of chemical-resistant glass 1 based on composite coating, except that modified phenolic resin 1 is replaced with phenolic resin 5, and other conditions remain unchanged, thus obtaining chemical-resistant glass 7 based on composite coating.

[0085] Table 1. Formulations of Application Examples 1-5 and Comparative Application Examples 1-2 (by weight)

[0086]

[0087] The following are the test methods for performance parameters involved in this invention:

[0088] 1. Nuclear magnetic resonance hydrogen spectrum test: Benzoxazole cyano modifier 1 and benzoxazole cyano alkenyl compound 1 were characterized by nuclear magnetic resonance spectroscopy instrument (Bruker AM-600, Advance 600).

[0089] 2. Fourier Transform Infrared Spectroscopy (FT-IR): Phenolic resin 1 was characterized using a Thermo Nicolet IS10 Fourier Transform Infrared Spectrometer; its main characteristic peaks are as follows: 3200~3600 cm⁻¹ -1 A broad OH stretching vibration absorption peak appears at 2920 cm⁻¹; -1 and 2850 cm -1 A saturated CH stretching vibration peak appears at 2250 cm⁻¹; -1 A sharp characteristic absorption peak of cyano appears at 1600 cm⁻¹; -1 and 1500 cm -1 Strong absorption bands belonging to the benzene ring skeleton and the C=N bond of the benzoxazole ring appear nearby; at 1250 and 1000 cm⁻¹ -1 Broad peaks of stretching vibrations of aromatic ethers at COC and C-OH were observed within the range. Among them, the peak at 2250 cm⁻¹ was [missing value]. -1 The cyano characteristic peak at the site confirmed that benzoxazole cyano modifier 1 had been successfully grafted onto the phenolic resin skeleton.

[0090] 3. Basic properties of the coating: The coating thickness is tested according to GB / T 1764-1979; the hardness is tested according to GB / T 6739-2006; the adhesion is tested according to GB / T 1720-1979; and the frontal impact resistance is tested according to GB / T 20624.1-2006.

[0091] 4. Corrosion resistance test: Test according to GB / T 9274-1988 and observe the changes in the appearance of the coating after 1500 h.

[0092] Table 2 Coating performance test results

[0093]

[0094] As shown in Table 2, the performance of Application Examples 1-5 is significantly better than that of Comparative Application Examples 1-2, proving that the coating of the chemical-resistant glass provided by this invention has better mechanical properties such as hardness, adhesion, and impact resistance. The introduction of benzoxazole and benzothiazole groups and cyano functional groups enhances the stability and chemical resistance of the crosslinking network. Comparative Application Example 1 uses 1,2-epoxyoctane to modify the phenolic resin, proving that epoxy functional groups with only flexible chains and lacking the rigid structure of benzoxazole cannot impart sufficient chemical resistance to the coating.

[0095] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A chemical-resistant glass based on a nanocomposite coating, characterized in that, This includes surface-treated glass and nanocomposite coatings applied to its upper and lower surfaces; The nanocomposite coating, by weight, comprises the following components: 30-35 parts epoxy resin, 25-35 parts modified phenolic resin, 3-5 parts nano pigments and fillers, 25-30 parts inactive diluent, 5-15 parts reactive diluent, and 0.5-1.5 parts additives; the modified phenolic resin is obtained by modifying phenolic resin with a benzo[a]heterocyclic cyano modifier, wherein the benzo[a]heterocyclic cyano modifier includes one or more of benzo[a]oxazole cyano modifier and benzo[a]thiazole cyano modifier; the structure of the benzo[a]oxazole cyano modifier is shown in Formula 1, and the structure of the benzo[a]thiazole cyano modifier is shown in Formula 2. Equation 1; Equation 2; where R in Equations 1 and 2 is a carbon chain with double bonds.

2. The chemical-resistant glass based on a nanocomposite coating as described in claim 1, characterized in that, The nano-pigment and filler are selected from one or more of nano-silica, nano-zirconia, nano-titanium oxide, nano-alumina, and nano-montmorillonite; the non-reactive diluent is selected from one or more of propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, cyclohexanone, and xylene; the reactive diluent is selected from one or more of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and ethylene glycol diglycidyl ether; the auxiliary agent is selected from one or more of polyether-modified polysiloxane, non-silicone defoamer, and polymeric dispersant; the molar ratio of phenolic resin to benzo[a]heterocyclic cyano modifier is 1:(0.95~1.05).

3. The chemical-resistant glass based on a nanocomposite coating as described in claim 1, characterized in that, The method for preparing the modified phenolic resin includes the following steps: Phenolic resin is mixed with solvent and heated and stirred until the resin is completely dissolved. The system is cooled to ≤50℃ and vacuum dehydrated until no bubbles are generated. Then the temperature is raised to 90~100℃. The benzo[a]heterocyclic cyano modifier is dissolved in solvent and placed in a constant pressure dropping funnel for later use. 0.2% of triphenylphosphine relative to the mass of the modifier is added directly to the phenolic resin solution and stirred to disperse it evenly. The benzo[a]heterocyclic cyano modifier solution is slowly added dropwise through the constant pressure dropping funnel. After the addition is complete, the reaction is refluxed. After the reaction is completed, the temperature is cooled to ≤30℃, and the modified phenolic resin is discharged and stored in a sealed container.

4. The chemical-resistant glass based on a nanocomposite coating as described in claim 1, characterized in that, The preparation method of the benzo[a]heterocyclic cyano modifier includes the following steps: (1) Synthesis of benzo[a]heterocyclic cyanoalkenyl compounds: An anhydrous toluene solution of 2-benzo[a]heterocyclic acetonitrile was prepared, and ammonium acetate and enaldehyde were added to the solution. The reaction mixture was then heated to reflux. After the reaction was completed, the benzo[a]heterocyclic cyanoalkenyl compounds were purified. (2) Synthesis of benzo[a]heterocyclic cyano modifier: Benzo[a]heterocyclic cyanoolefin compound, (S)-6,6'-bis(9-anthrayl)spirocyclodiol phosphate and magnesium sulfate were mixed, toluene was added, and hydrogen peroxide aqueous solution was added dropwise. After the reaction was completed, the benzo[a]heterocyclic cyano modifier was obtained by purification.

5. The chemical-resistant glass based on a nanocomposite coating as described in claim 4, characterized in that, The enal is selected from one or more of 6-nonenal, 5-octenal, 4-heptenal, 3-hexenal, and 3-pentenal.

6. The method for preparing chemical-resistant glass based on nanocomposite coating as described in claim 1, characterized in that, Includes the following steps: S1. Preparation of two-component coating: A portion of the non-reactive diluent and the reactive diluent are poured into the dispersion tank of a high-speed stirred sand mill disperser. Cooling water is connected to the dispersion tank, and bisphenol A epoxy resin is slowly added while stirring at a slow speed. Then, the speed of the high-speed stirred sand mill disperser is increased, and the temperature is kept ≤50℃ to prepare a completely dissolved bisphenol A epoxy resin solution, which is coating component A. Modified phenolic resin, additives and the remaining non-reactive diluent are added to a new dispersion tank and stirred evenly. Nano pigment and filler powder is slowly added in batches. The speed is increased and then grinding beads are added for grinding and dispersion. Large agglomerates that have not been dispersed are removed by centrifugal sedimentation. The upper uniform slurry is used to obtain coating component B. After filtering the paint component A through a filter screen, it is mixed with the centrifuged paint component B in a certain proportion, degassed under high vacuum, and then poured into a spray gun for later use after standing. S2. Coating application and curing: The glass substrate is ultrasonically cleaned, dried with nitrogen, and then immersed in an ethanol aqueous solution of epoxy silane coupling agent. After removal, it is cured and then kept warm. In a clean environment, the coating is sprayed onto the treated glass surface, spraying from top to bottom, keeping the spray gun at a consistent distance from the glass surface to obtain a coating with uniform film thickness. After the coating is completed, the glass substrate is transferred to an oven for gradient curing to obtain chemical-resistant glass based on the composite coating.

7. The method for preparing chemical-resistant glass based on a nanocomposite coating as described in claim 6, characterized in that, The gradient curing method involves holding the temperature at 75-85℃ for 50-70 min, then raising the temperature to 110-130℃ at a rate of 1-2℃ / min and holding for 50-70 min, then raising the temperature to 145-155℃ at the same rate and holding for 100-120 min, and finally holding at 155-165℃ for 100-120 min.

8. The chemical-resistant glass based on nanocomposite coating prepared by the preparation method of the chemical-resistant glass based on nanocomposite coating as described in any one of claims 1 to 5, or the chemical-resistant glass based on nanocomposite coating as described in any one of claims 6 to 7, is used as a chemical-resistant glass in the fields of industrial chemical industry, medical and biotechnology, and household and daily consumer products.

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