A lead-free porcelain-like glass wine bottle and a preparation process thereof

Abstract

This invention discloses a lead-free imitation porcelain glass wine bottle and its preparation process, belonging to the field of glass product processing technology. The preparation process of the glass wine bottle includes the following steps: (1) Weighing by weight: 45-55 parts of quartz sand, 7-9 parts of soda ash, 10-15 parts of calcite, 6-10 parts of talc, 3-5 parts of alumina, 1.5-2.5 parts of opacifier, 0.5-1 part of clarifying agent, 4-6 parts of nucleating agent, and 1-2.5 parts of fluxing accelerator; (2) Mixing the above raw materials in a mixer to obtain a batch material, melting and homogenizing the batch material, and injecting it into a mold to form a glass bottle blank; (3) Annealing the glass bottle blank in an annealing furnace, cooling, cleaning, and drying; (4) Spraying a silica coating liquid onto the surface of the glass bottle; curing and cooling to obtain the glass bottle. The glass wine bottle prepared by this invention has the properties of small scratch depth, low wear rate, high flexural strength, and low ultraviolet transmittance.

Description

Technical Field

[0001] This invention relates to the field of glass processing technology, specifically to a lead-free imitation porcelain glass wine bottle and its preparation process. Background Technology

[0002] Lead-free imitation porcelain glass bottles are glass containers made primarily from silica sand, soda ash, and feldspar, through high-temperature melting, molding, and annealing processes. Their composition completely eliminates harmful elements such as lead and arsenic, combining the aesthetics of ceramics with the dense structure and high strength of glass. They are mainly used in high-end baijiu, fruit wines, and health wines. However, lead-free imitation porcelain glass bottles face surface damage issues in practical applications. During cleaning, filling, and storage and transportation, friction and collisions between bottles or with equipment can easily cause scratches and wear. These surface defects not only affect the appearance but also form micro-cracks, weakening the bottle's strength and impact resistance, increasing the risk of breakage and leakage, and causing product loss. Currently, the industry mainly uses organic polymer coatings, tempering treatments, or formula modification to address these problems. However, organic coatings have poor adhesion and are prone to aging and peeling; tempering treatments cannot effectively prevent surface scratches and shatter upon breakage; formula modification affects the imitation porcelain appearance, and the process is complex and costly. In recent years, spraying technology has been widely used in the field of glass surface protection because it forms a protective film by uniformly applying functional coatings to the glass surface. This process has advantages such as simple process, uniform film formation and strong applicability. It can give the surface excellent protective ability without changing the properties of the glass itself, and does not affect the original appearance of the glass.

[0003] Chinese invention patent CN114804625A discloses a Mars Green glass bottle and its preparation method. The Mars Green glass bottle comprises the following raw materials in parts by weight: 540-580 parts quartz sand, 180-220 parts soda ash, 150-200 parts calcite, 120-160 parts feldspar, 15-20 parts copper oxide, 480-550 parts crushed glass, and 23-42 parts composite modifier. The glass bottle produced by this invention exhibits excellent resistance to internal pressure and impact, but its abrasion resistance still needs improvement. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a lead-free imitation porcelain glass wine bottle and its manufacturing process.

[0005] A manufacturing process for a lead-free imitation porcelain glass wine bottle includes the following steps: (1) Weigh out the following by weight: 45-55 parts of quartz sand, 7-9 parts of soda ash, 10-15 parts of calcite, 6-10 parts of talc, 3-5 parts of alumina, 1.5-2.5 parts of opacifier, 0.5-1 part of clarifying agent, 4-6 parts of nucleating agent, and 1-2.5 parts of fluxing accelerator; (2) The above raw materials are mixed in a mixer to obtain a batch material. The batch material is melted and kept warm and homogenized, and then injected into a mold to form a glass bottle preform. (3) Anneal the glass preform in an annealing furnace, cool, clean and dry to obtain a glass bottle; (4) Spray a silica coating liquid onto the surface of the glass bottle; cure and cool to obtain a lead-free imitation porcelain glass wine bottle; The silica coating solution comprises the following raw materials in parts by weight: 30-50 parts of nano silica sol, 4-6 parts of coupling agent, and 15-20 parts of deionized water. The structural formula of the coupling agent is as follows: .

[0006] The coupling agent is prepared by the following method: S1: 1-Chloromethylpyrene reacts with 3,3'-oxadiphenylamine to give intermediate 1. S2: Intermediate 1 reacts with 3-chloropropyltriethoxysilane to give a coupling agent.

[0007] The emulsifier is sodium fluorosilicate.

[0008] The clarifying agent is sodium sulfate.

[0009] The nucleating agent is composed of titanium oxide and zirconium oxide mixed in a weight ratio of 2:(2-4).

[0010] The fluxing accelerator is composed of sodium phosphate and borax mixed in a weight ratio of 2:(2-3).

[0011] In step (2), the melting temperature is 1450-1480℃ and the melting time is 3-4h.

[0012] In step (3), the annealing process is as follows: the temperature is lowered to 450-500℃ at a rate of 2-4℃ / min, and then lowered to 300-350℃ at a rate of 2-4℃ / min.

[0013] In step (4), the spraying pressure is 0.35-0.55 MPa; the spraying distance is 20-28 cm.

[0014] A lead-free imitation porcelain glass wine bottle is produced by the above-mentioned process.

[0015] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The lead-free imitation porcelain glass wine bottle prepared by this invention has the properties of small scratch depth, low wear rate, high flexural strength and low ultraviolet transmittance. Attached Figure Description

[0016] Figure 1The 1H NMR spectrum of the coupling agent prepared in Example 1; Figure 2 High-resolution mass spectrum of the coupling agent prepared in Example 1; Figure 3 The Fourier transform infrared spectrum of the coupling agent prepared in Example 1 is shown. Detailed Implementation

[0017] Example 1 Preparation of Coupling Agent S1: Under ice bath conditions, add 300 mL of anhydrous DMF, 0.1 mol of 3,3'-oxadiphenylamine, and 0.21 mol of potassium carbonate to a reaction flask, stir to mix, add 0.205 mol of 1-chloromethylpyrene, react at room temperature for 3 h, filter, slowly pour into 1000 mL of deionized water, stir to precipitate; filter, wash three times with deionized water (50 mL each time), add 200 mL of cold anhydrous diethyl ether, stir at room temperature for 30 min, filter, wash with 50 mL of cold anhydrous diethyl ether, dry under vacuum at 60 °C for 12 h to obtain intermediate 1; the reaction equation is shown below:

[0018] Its 1H NMR data are as follows 1 H NMR (400 MHz, DMSO- d 6 ) δ 8.07 (dd, J = 8.3, 3.6Hz, 2H), 8.05 – 8.00 (m, 6H), 7.98 – 7.94 (m, 4H), 7.79 – 7.68 (m, 4H), 7.32(dq, J = 8.3, 2.7 Hz, 2H), 7.22 (t, J = 7.8 Hz, 2H), 6.81 (ddd, J = 7.7, 2.2,1.2 Hz, 2H), 6.67 (ddd, J = 7.9, 2.1, 1.2 Hz, 2H), 6.33 (t, J = 5.3 Hz, 2H), 6.28 (t, J = 2.1 Hz, 2H), 4.88 (d, J = 5.4 Hz, 4H); HRMS (m / z): 629.2513[M+H] + ; S2: Under nitrogen protection, 400 ml of anhydrous acetonitrile and 0.1 mol of intermediate 1 were added to a reaction flask and stirred until well mixed. Then, 0.01 mol of potassium iodide and 0.21 mol of triethylamine were added, followed by slow dropwise addition of 0.21 mol of 3-chloropropyltriethoxysilane. The addition was completed over 20 min. The mixture was heated to 70 °C and reacted for 7 h. After cooling to room temperature, the mixture was filtered and evaporated at 60 °C to constant weight. The mixture was recrystallized from 300 ml of anhydrous n-hexane, filtered, and dried under vacuum at 60 °C for 12 h to obtain the coupling agent. The reaction equation is shown below:

[0019] Its proton nuclear magnetic resonance spectrum is as follows Figure 1 As shown, its 1H NMR spectrum data are as follows: 1 H NMR (400 MHz, DMSO- d 6 )δ 8.08 (dd, J = 8.2, 3.3 Hz, 2H), 8.06 – 8.02 (m, 6H), 7.97 (d, J = 8.4 Hz,4H), 7.78 – 7.67 (m, 4H), 7.26 (ddd, J = 8.5, 2.2, 1.7 Hz, 2H), 7.18 (t, J =7.9 Hz, 2H), 6.87 – 6.81 (m, 4H), 6.49 (t, J = 2.2 Hz, 2H), 4.69 (s, 4H), 3.81 (q, J = 7.5 Hz, 12H), 3.38 (t, J = 7.1 Hz, 4H), 1.63 (tt, J = 9.5, 7.1 Hz, 4H), 1.21 (t, J = 7.5 Hz, 18H), 0.78 (t, J = 9.5 Hz, 4H); its high-resolution mass spectrum is as follows: Figure 2 As shown, HRMS (m / z): 1037.4882 [M+H] + .

[0020] Figure 3 The Fourier transform infrared spectrum of the coupling agent prepared in Example 1 is shown in the figure. As can be seen from the figure, the sample exhibits a high optical density at 3060 cm⁻¹. -1 The nearby values ​​belong to the CH stretching vibration of aromatic rings, indicating that the molecule contains aromatic structures such as pyrene and benzene rings. (2973 cm⁻¹) -1 and 2874cm -1 The nearby peaks, attributed to aliphatic CH stretching vibrations, indicate the presence of a propyl chain and an ethoxy group in the molecule; 1603 cm⁻¹ -1 and 1510cm -1The nearby absorption peak is attributed to the skeletal vibration of the aromatic ring; 1320 cm⁻¹ -1 and 1248cm -1 The nearby absorption peak corresponds to the CN stretching vibration; 1104 cm⁻¹ -1 The strong absorption peak nearby is due to the Si-OC stretching vibration, 956 cm⁻¹. -1 The nearby absorption peaks are characteristic absorption peaks of Si-OEt.

[0021] Example 2 Preparation of silica coating solution (1) Take 150g of deionized water and adjust the pH to 4.0 with acetic acid; (2) Add 40g of coupling agent (prepared in Example 1) to 200ml of anhydrous ethanol, heat to 25℃, and stir until completely dissolved to obtain an ethanol solution of coupling agent; (3) Slowly add the deionized water prepared in step (1) to the coupling agent ethanol solution. After 20 min, continue stirring for 30 min. Then slowly add 300 g of nano silica sol. After 30 min, continue stirring for 30 min to mix thoroughly. Stop stirring and let it stand at room temperature for 12 h. First filter with filter paper with a pore size of 10 μm, and then filter with a 0.45 μm filter membrane to obtain the silica coating solution.

[0022] Example 3 Preparation of silica coating solution (1) Take 180g of deionized water and adjust the pH to 4.0 with acetic acid; (2) Add 50g of coupling agent (prepared in Example 1) to 200ml of anhydrous ethanol, heat to 30℃, and stir until completely dissolved to obtain an ethanol solution of coupling agent; (3) Slowly add the deionized water prepared in step (1) to the coupling agent ethanol solution. After 20 min, continue stirring for 30 min. Then slowly add 400 g of nano silica sol. After 30 min, continue stirring for 30 min to mix thoroughly. Stop stirring and let it stand at room temperature for 12 h. First filter with filter paper with a pore size of 10 μm, and then filter with a 0.45 μm filter membrane to obtain the silica coating solution.

[0023] Example 4 Preparation of silica coating solution (1) Take 200g of deionized water and adjust the pH to 4.0 with acetic acid; (2) Add 60g of coupling agent (prepared in Example 1) to 200ml of anhydrous ethanol, heat to 35℃, and stir until completely dissolved to obtain an ethanol solution of coupling agent; (3) Slowly add the deionized water prepared in step (1) to the coupling agent ethanol solution. After 20 min, continue stirring for 30 min. Then slowly add 500 g of nano silica sol. After 30 min, continue stirring for 30 min to mix thoroughly. Stop stirring and let it stand at room temperature for 12 h. First filter with filter paper with a pore size of 10 μm, and then filter with a 0.45 μm filter membrane to obtain the silica coating solution.

[0024] Example 5: Preparation of Lead-Free Imitation Porcelain Glass Wine Bottles (1) Weigh out: 450g of quartz sand, 70g of soda ash, 100g of calcite, 60g of talc powder, 30g of alumina, 15g of opacifier (sodium fluorosilicate), 5g of clarifying agent (sodium sulfate), 40g of nucleating agent (20g of titanium dioxide, 20g of zirconium oxide), and 10g of fluxing accelerator (5g of sodium phosphate, 5g of borax). (2) The above raw materials are fed into a mixer and stirred at 200 r / min for 30 min to obtain a batch. The batch is fed into a glass melting furnace and melted at 1450℃ for 4 h to obtain glass melt. The glass melt is kept at 1450℃ for 3 h and then cooled to 1100℃. It is then injected into a wine bottle mold preheated to 550℃ and formed by small-mouth pressure blowing: first, the glass is pressed into a bottle preform with a pressing pressure of 0.5 MPa for 4 s; then the bottle preform is transferred to the forming mold and compressed air is introduced with a blowing pressure of 0.6 MPa for 6 s, so that the glass melt adheres tightly to the forming mold cavity to obtain a glass bottle preform. (3) The glass bottle preform is sent into a gradient annealing furnace for annealing: first, it is kept at 580℃ for 2 hours, then cooled to 500℃ at a rate of 2℃ / min, then cooled to 350℃ at a rate of 2℃ / min, and finally cooled to room temperature naturally to obtain a glass bottle; then the glass bottle is sprayed with deionized water for cleaning, then ultrasonically cleaned at 40kHz for 5 minutes, rinsed with deionized water 3 times, and the glass bottle is placed in a drying oven and dried at 100℃ for 20 minutes. (4) A silica coating liquid (prepared in Example 2) was uniformly coated on the surface of the glass bottle by air spraying. The spraying parameters were: spray gun pressure 0.35 MPa, distance between the spray gun and the bottle body 20 cm, and spray thickness 10 μm. After spraying, the bottle was placed in a constant temperature hot air circulating oven and pre-baked at 100°C for 10 min. Then the temperature was raised to 200°C and kept at that temperature for 60 min. The bottle was then naturally cooled to room temperature to obtain a lead-free imitation porcelain glass wine bottle.

[0025] Example 6: Preparation of Lead-Free Imitation Porcelain Glass Wine Bottles (1) Weigh out: 500g of quartz sand, 80g of soda ash, 120g of calcite, 80g of talc, 40g of alumina, 20g of opacifier (sodium fluorosilicate), 8g of clarifying agent (sodium sulfate), 50g of nucleating agent (20g of titanium dioxide, 30g of zirconium oxide), and 18g of fluxing accelerator (8g of sodium phosphate, 10g of borax); (2) The above raw materials are fed into a mixer and stirred at 200 r / min for 30 min to obtain a batch. The batch is fed into a glass melting furnace and melted at 1460℃ for 3.5 h to obtain glass melt. The glass melt is kept at 1460℃ for 3 h, then cooled to 1100℃ and injected into a wine bottle mold preheated to 550℃. The small-mouth pressure blowing method is used for forming: first, the glass is pressed into a bottle preform with a pressing pressure of 0.5 MPa for 4 s; then the bottle preform is transferred to the forming mold and compressed air is introduced with a blowing pressure of 0.6 MPa for 6 s, so that the glass melt adheres tightly to the forming mold cavity to obtain a glass bottle preform. (3) The glass bottle preform is sent into a gradient annealing furnace for annealing: first, it is kept at 580℃ for 2 hours, then cooled to 480℃ at a rate of 3℃ / min, then cooled to 320℃ at a rate of 3℃ / min, and finally cooled to room temperature naturally to obtain a glass bottle. Then, the glass bottle is sprayed with deionized water for cleaning, then ultrasonically cleaned at 40kHz for 5 minutes, rinsed with deionized water 3 times, and the glass bottle is placed in a drying oven and dried at 100℃ for 20 minutes. (4) A silica coating liquid (prepared in Example 3) was uniformly coated on the surface of the glass bottle by air spraying. The spraying parameters were: spray gun pressure 0.45 MPa, distance between the spray gun and the bottle body 25 cm, and spray thickness 10 μm. After spraying, the bottle was placed in a constant temperature hot air circulating oven and pre-baked at 100°C for 10 min. Then the temperature was raised to 200°C and kept at that temperature for 60 min. The bottle was then naturally cooled to room temperature to obtain a lead-free imitation porcelain glass wine bottle.

[0026] Example 7: Preparation of Lead-Free Imitation Porcelain Glass Wine Bottles (1) Weigh out: 550g of quartz sand, 90g of soda ash, 150g of calcite, 100g of talc powder, 50g of alumina, 25g of opacifier (sodium fluorosilicate), 10g of clarifying agent (sodium sulfate), 60g of nucleating agent (20g of titanium dioxide, 40g of zirconium oxide), and 25g of fluxing accelerator (10g of sodium phosphate, 15g of borax); (2) The above raw materials are fed into a mixer and stirred at 200 r / min for 30 min to obtain a batch. The batch is fed into a glass melting furnace and melted at 1480℃ for 3 h to obtain molten glass. The molten glass is kept at 1480℃ for 3 h and then cooled to 1100℃. It is then injected into a wine bottle mold preheated to 550℃ and formed by small-mouth pressure blowing: first, the glass is pressed into a bottle preform with a pressing pressure of 0.5 MPa for 4 s; then the bottle preform is transferred to the forming mold and compressed air is introduced with a blowing pressure of 0.6 MPa for 6 s, so that the molten glass adheres tightly to the forming mold cavity to obtain a glass bottle preform. (3) The glass bottle preform is sent into a gradient annealing furnace for annealing: first, it is kept at 580℃ for 2 hours, then cooled to 450℃ at a rate of 4℃ / min, then cooled to 300℃ at a rate of 4℃ / min, and finally cooled to room temperature naturally to obtain a glass bottle. Then, the glass bottle is sprayed with deionized water for cleaning, then ultrasonically cleaned at 40kHz for 5 minutes, rinsed with deionized water 3 times, and the glass bottle is placed in a drying oven and dried at 100℃ for 20 minutes. (4) A silica coating liquid (prepared in Example 4) was uniformly coated on the surface of the glass bottle by air spraying. The spraying parameters were: spray gun pressure 0.55 MPa, distance between the spray gun and the bottle body 28 cm, and spray thickness 10 μm. After spraying, the bottle was placed in a constant temperature hot air circulating oven and pre-baked at 100°C for 10 min. Then the temperature was raised to 200°C and kept at that temperature for 60 min. The bottle was then naturally cooled to room temperature to obtain a lead-free imitation porcelain glass wine bottle.

[0027] Comparative Example 1 The raw material composition and preparation method of the lead-free imitation porcelain glass wine bottle are basically the same as those in Example 6, except that the silica coating solution is replaced with an equal weight of silica coating solution prepared by the following method: The preparation method of the silica coating solution is basically the same as that in Example 3, except that 1-chloromethylpyrene in the coupling agent step S1 is replaced with an equimolar amount of 1-chloromethylnaphthalene.

[0028] Comparative Example 2 The raw material composition and preparation method of the lead-free imitation porcelain glass wine bottle are basically the same as those in Example 6, except that the silica coating solution is replaced with an equal weight of silica coating solution prepared by the following method: The preparation method of the silica coating solution is basically the same as that in Example 3, except that the 3,3'-oxadiphenylamine in the coupling agent preparation step S1 is replaced with an equimolar amount of 3,3'-methylenediphenylamine.

[0029] Comparative Example 3 The raw material composition and preparation method of the lead-free imitation porcelain glass wine bottle are basically the same as those in Example 6, except that the silica coating solution is replaced with an equal weight of silica coating solution prepared by the following method: The preparation method of the silica coating solution is basically the same as that in Example 3. The difference is that the 3,3'-oxadiphenylamine in the coupling agent preparation step S1 is replaced with an equimolar amount of 3-phenoxyaniline, the amount of 1-chloromethylpyrene is 0.105 mol, and the amount of 3-chloropropyltriethoxysilane in step S2 is 0.11 mol.

[0030] Comparative Example 4 The raw material composition and preparation method of the lead-free imitation porcelain glass wine bottle are basically the same as those in Example 6, except that the silica coating solution is replaced with an equal weight of silica coating solution prepared by the following method: The preparation method of the silica coating solution is basically the same as that in Example 3, except that the coupling agent is replaced with an equal weight of 3-chloropropyltriethoxysilane.

[0031] Comparative Example 5 The raw material composition and preparation method of the lead-free imitation porcelain glass wine bottle are basically the same as those in Example 6, except that the silica coating solution is replaced with an equal weight of silica coating solution prepared by the following method: (1) Take 180g of deionized water and adjust the pH to 4.0 with acetic acid; (2) Slowly add the deionized water prepared in step (1) to 400g of nano silica sol. After 30min, continue stirring for 30min to mix thoroughly. Stop stirring and let it stand at room temperature for 12h. First filter with filter paper with a pore size of 10μm, and then filter with a 0.45μm filter membrane to obtain silica coating solution.

[0032] Comparative Example 6 The raw material composition and preparation method of the lead-free imitation porcelain glass wine bottle are basically the same as those in Example 6, except that the silica coating solution is replaced with an equal weight of silica coating solution prepared by the following method: (1) Take 180g of deionized water and adjust the pH to 4.0 with acetic acid; (2) Add 80g of coupling agent (prepared in Example 1) to 200ml of anhydrous ethanol, heat to 30℃, and stir until completely dissolved to obtain an ethanol solution of coupling agent; (3) Slowly add the deionized water prepared in step (1) to the coupling agent ethanol solution. After 20 min, continue stirring for 30 min. Then slowly add 400 g of nano silica sol. After 30 min, continue stirring for 30 min to mix thoroughly. Stop stirring and let it stand at room temperature for 12 h. First filter with filter paper with a pore size of 10 μm, and then filter with a 0.45 μm filter membrane to obtain the silica coating solution.

[0033] The quartz sand used in the embodiments and comparative examples of this application has a particle size distribution of 70-80 mesh and is produced by Anhui Fengyang Zhongyang Quartz Sand Co., Ltd.; the calcite has a particle size distribution of 300-325 mesh and is produced by Neixiang Baotianman Non-metallic Mining Co., Ltd.; the talc powder has an average particle size of 20 μm and is produced by Guilin Guiguang Talc Development Co., Ltd.; the alumina is of type BM-12D with D90=8.20 μm and is produced by Shandong Hengjia High Purity Aluminum Industry Technology Co., Ltd.; the titanium dioxide is anatase nano-titanium dioxide with D50=20 nm and is produced by Nanjing Aipuri Nanomaterials Co., Ltd.; the zirconium oxide is of type JK-3Y-ZN and is produced by Zhejiang Jinkun Zirconium Industry Co., Ltd.; the borax is pentahydrate borax; and the nano-silica sol is of type HA3010. It contains 30 wt% of the substance and is produced by Shandong Baite New Materials Co., Ltd.

[0034] The lead-free imitation porcelain glass wine bottles prepared in the examples and comparative examples were subjected to performance tests, and the test results are shown in Table 1.

[0035] Sample preparation: Clean and dry the glass bottle, and cut a 200mm×100mm×5mm sample from a flat part of the bottle.

[0036] Scratch depth: A constant load scratch test was conducted using a multi-functional material surface performance tester (MFT4000, Lanzhou Huahui Instrument Technology Co., Ltd.). The constant load was 21N, the loading speed was 10N / s, and the scratch length was set to 5mm during the test. The scratch depth was then observed.

[0037] Wear rate: The wear rate was tested using an HDR-2M reciprocating friction and wear testing machine with a ball-disc contact configuration and a pair of balls on top. The machine was subjected to reciprocating friction for 5 minutes under a load of 5N, a frequency of 5Hz, and a friction distance of 150mm. The friction trajectory was then scanned using an RtecMFT-5000 multi-functional friction testing machine to obtain the three-dimensional data of the wear tracks. The data was analyzed using Gwyddion three-dimensional analysis software to obtain the wear volume, and the wear rate was calculated using the following formula: ; In the formula, δ is the volumetric wear rate (mm). 3 / N·m), V is the wear volume (mm²) obtained from data analysis software. 3); s is the total friction distance (m); L is the load (N).

[0038] Flexural strength: The flexural strength of the specimens was measured using the three-point bending method. The instrument used was a KZY-300 flexural testing machine (Tianjin Luda Construction Instrument Co., Ltd.). The flexural strength was calculated using the following formula: ; In the formula, P is the flexural strength of the specimen (MPa), F is the maximum load when the specimen breaks (N), L is the distance between the two support points, i.e., the span (mm), b is the width of the specimen fracture (mm), and h is the height of the specimen fracture (mm).

[0039] Transmittance: Transmittance was measured using a UV-Vis spectrophotometer. The scanning wavelength range was set to 280-400 nm with a scanning interval of 5 nm. The transmittance at each wavelength was recorded, and the average transmittance (T) in the 280-400 nm band was calculated.

[0040] Anti-aging performance test: The sample was placed in a QUV accelerated aging test chamber for aging test, with an irradiation wavelength of 310nm and an irradiation intensity of 0.89W / m. 2 The glass bottles were aged at 60℃ for 800 hours, and their transmittance was tested again after aging. The rate of change in transmittance was calculated. .

[0041] Table 1 Performance Test Data of Lead-Free Imitation Porcelain Glass Wine Bottles

[0042] As can be seen from the data in Table 1, the lead-free imitation porcelain glass wine bottle prepared by the present invention has the properties of small scratch depth, low wear rate, high flexural strength and low ultraviolet transmittance.

[0043] The coupling agent prepared in this invention simultaneously contains a pyrene ring, a diphenyl ether structure, and a triethoxysilane functional group. The pyrene ring possesses a large π-conjugated system, which can form π-hydrogen bonds with the hydroxyl groups on the surface of nano-silica for synergistic adsorption, significantly improving the anchoring efficiency of the coupling agent on the inorganic particle surface. The ether bond (diphenyl ether structure) located between the two benzene rings breaks the steric hindrance of the rigid aromatic ring, enhancing the flexibility and polarity of the coupling agent's molecular skeleton. This allows the coupling agent to be more uniformly dispersed and coated on the silica particle surface during hydrolysis and condensation, facilitating the formation of a continuous and dense organic-inorganic composite interface structure. In the silica coating solution… During the formulation stage, the triethoxysilyl groups at the end of the coupling agent first undergo hydrolysis to generate silanols (-Si-OH). Subsequently, during the solution mixing and post-coating thermosetting stages, these silanols play a dual role: on the one hand, they undergo dehydration condensation with the silanol groups on the surface of the nano-silica particles to form stable Si-O-Si covalent bonds, achieving a strong chemical connection between the coupling agent and the particles; on the other hand, some free silanol groups undergo self-condensation to construct a three-dimensional cross-linked network structure, bridging the dispersed silica particles and thus improving the structural stability and film continuity of the sol system. During the film formation process, the coupling agent promotes the formation of a highly ordered, dense film structure with few defects through the synergistic effect of intermolecular π-π stacking and hydrogen bonding. This significantly improves the hardness and scratch resistance of the film, reducing scratch depth and wear rate; on the other hand, the formation of a continuous bonding layer between the film and the glass substrate effectively inhibits the initiation and propagation of microcracks, thereby improving the flexural strength of the glass bottle.

[0044] Furthermore, the coupling agent prepared in this invention significantly reduces the transmittance of coated glass bottles in the ultraviolet band through the synergistic effect of the pyrene ring, ether bond, and triethoxysilane. The pyrene ring possesses a large π-conjugated structure, exhibiting strong absorption characteristics in the 280-400 nm ultraviolet region, effectively capturing incident ultraviolet light energy. The ether bond imparts suitable flexibility and polarity to the coupling agent molecular chain, facilitating the formation of a uniform and dense coating layer on the surface of nano-silica particles, thereby reducing localized light-transmitting areas caused by particle agglomeration or coating defects. The synergistic effect of these two components creates a continuous and dense optical barrier in the ultraviolet region, effectively reducing the average transmittance and thus endowing the glass bottles with excellent ultraviolet protection.

[0045] In Comparative Example 2, the ether bond (-O-) in the coupling agent was replaced with a methylene bond (-CH2-), which reduced the flexibility and hydrophilicity of the coupling agent molecule, decreased its compatibility and bonding efficiency with silica sol, and resulted in poorer film density and more micro-defects after curing. Simultaneously, the weakened interfacial adhesion made the coating more susceptible to scratches and wear under friction or stress, leading to a decrease in flexural strength.

[0046] In Comparative Example 3, the coupling agent molecule changed from a di-secondary amine structure to a mono-secondary amine structure, resulting in a reduction in the number of crosslinkable silane functional groups in the coupling agent, a decrease in chemical bonding sites with silica sol, a lower crosslinking density in the coating layer, and a looser structure. Furthermore, the shorter molecular chain segments lack sufficient multi-point anchoring, weakening the adhesion between the film layer and the glass substrate, thus increasing scratch depth, wear rate, and flexural strength.

[0047] Comparative Example 4 uses only 3-chloropropyltriethoxysilane, which has a simple molecular structure containing only silane groups and lacks large π-conjugated structures such as pyrene groups and flexible aromatic ether segments. This makes it difficult to form effective π-π stacking and steric hindrance effects, resulting in insufficient dispersion and orderly assembly of silica particles. Although it can form Si-O-Si bonds with the glass surface, the constructed network structure is relatively simple and has poor density. The film is prone to defects and microcracks, which reduces both wear resistance and flexural strength.

[0048] In Comparative Example 5, the absence of a coupling agent resulted in a lack of chemical bonding bridges between the silica coating solution and the glass substrate, relying solely on physical adsorption for adhesion, which significantly reduced interfacial adhesion. Under external forces, the film layer was prone to peeling, scratches, and abrasion, failing to effectively protect the glass substrate. Consequently, scratch depth increased, abrasion rate rose, and flexural strength decreased.

[0049] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A manufacturing process for a lead-free imitation porcelain glass wine bottle, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 45-55 parts of quartz sand, 7-9 parts of soda ash, 10-15 parts of calcite, 6-10 parts of talc, 3-5 parts of alumina, 1.5-2.5 parts of opacifier, 0.5-1 part of clarifying agent, 4-6 parts of nucleating agent, and 1-2.5 parts of fluxing accelerator; (2) The above raw materials are mixed in a mixer to obtain a batch material. The batch material is melted and kept warm and homogenized, and then injected into a mold to form a glass bottle preform. (3) Anneal the glass preform in an annealing furnace, cool, clean and dry to obtain a glass bottle; (4) Spray a silica coating liquid onto the surface of the glass bottle, cure it, and cool it to obtain a lead-free imitation porcelain glass wine bottle; The silica coating solution comprises the following raw materials in parts by weight: 30-50 parts of nano silica sol, 4-6 parts of coupling agent, and 15-20 parts of deionized water. The structural formula of the coupling agent is as follows: 。 2. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, The coupling agent is prepared by the following method: S1: 1-Chloromethylpyrene reacts with 3,3'-oxadiphenylamine to give intermediate 1. S2: Intermediate 1 reacts with 3-chloropropyltriethoxysilane to give a coupling agent.

3. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, The emulsifier is sodium fluorosilicate.

4. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, The clarifying agent is sodium sulfate.

5. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, The nucleating agent is composed of titanium oxide and zirconium oxide mixed in a weight ratio of 2:(2-4).

6. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, The fluxing accelerator is composed of sodium phosphate and borax mixed in a weight ratio of 2:(2-3).

7. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, In step (2), the melting temperature is 1450-1480℃ and the melting time is 3-4h.

8. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, In step (3), the annealing process is as follows: the temperature is lowered to 450-500℃ at a rate of 2-4℃ / min, and then lowered to 300-350℃ at a rate of 2-4℃ / min.

9. The manufacturing process of a lead-free imitation porcelain glass wine bottle according to claim 1, characterized in that, In step (4), the spraying pressure is 0.35-0.55 MPa; the spraying distance is 20-28 cm.

10. A lead-free imitation porcelain glass wine bottle, characterized in that, It is prepared by the process described in any one of claims 1-9.

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