High-strength tempered glass vessel and preparation process thereof

Abstract

The invention relates to the technical field of tempered glass, in particular to a high-strength tempered glass vessel and a preparation process thereof. The preparation method comprises the following steps: uniformly mixing organic silicon modified acrylate, organic silicon modified polyurethane, a polydimethylsiloxane modifier, ammonium sulfate, polyethylene glycol, melamino-formaldehyde resin and deionized water to obtain enhanced spraying liquid; and when the tempered glass ware is cooled to 175-185 DEG C, spraying the tempered glass ware and cooling gas on the surface of the tempered glass ware to obtain the high-strength tempered glass ware.

Description

Technical Field

[0001] The invention relates to the technical field of tempered glass, in particular to a high-strength tempered glass container and a preparation process thereof. Background Art

[0002] Tempered glass is a type of safety glass and a prestressed glass. In order to increase the strength of the glass, chemical or physical methods are usually used to form compressive stress on the glass surface. When the glass is subjected to external force, the surface stress is first offset, thereby increasing its bearing capacity and enhancing the glass's own resistance to wind pressure, cold and heat, impact, etc.

[0003] In addition, after tempering, the crystal structure of the nickel sulfide grains inside the tempered glass will change over time. During the transformation, the volume of the lattice will increase, and internal stress will be generated around it. When the internal stress accumulates to a certain level, it may cause the tempered glass to explode. In order to prevent the tempered glass from exploding during use, it is usually necessary to put the tempered glass into a homogenizing furnace for homogenization. Through the principle of hot dipping in the homogenizing furnace, the residual nickel sulfide can be eliminated, thereby improving the strength of the tempered glass.

[0004] Based on this, the present invention will provide a preparation process of high-strength tempered glassware to further improve the strength of the tempered glassware. Summary of the invention

[0005] The object of the present invention is to provide a high-strength tempered glass container and a preparation process thereof, so as to solve the problems raised in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions: A preparation process of high-strength tempered glassware comprises the following steps: S1: Evenly mix organosilicon-modified acrylate, organosilicon-modified polyurethane, polydimethylsiloxane modification, ammonium sulfate, polyethylene glycol, melamine formaldehyde resin, and deionized water to obtain an enhanced spraying liquid; S2: homogenize the tempered glassware; S21: placing the tempered glassware after the tempering treatment into a homogenizing furnace for heating treatment; S22: After the heating process is completed, a heat preservation process is performed; S23: After the heat preservation treatment is completed, a cooling treatment is performed to obtain a high-strength tempered glass container.

[0007] Furthermore, the enhanced spray liquid includes the following components: by weight, 40-50 parts of silicone-modified acrylate, 15-25 parts of silicone-modified polyurethane, 10-20 parts of modified polydimethylsiloxane, 3-6 parts of ammonium sulfate, 5-10 parts of polyethylene glycol, 4-8 parts of melamine formaldehyde resin, and 50 parts of deionized water.

[0008] Furthermore, the silicone-modified acrylate model is 8840, purchased from Shenzhen Haineng Chemical Co., Ltd.

[0009] Furthermore, the preparation method of the silicone-modified polyurethane is as follows: (1) under nitrogen protection, isophorone diisocyanate, polytetramethylene glycol, and hydroxypropyl-terminated polydimethylsiloxane are added to a reaction kettle, stirred and heated to 70-150° C. for reflux reaction for a period of time until the isocyanate group content in the reaction system no longer changes, and then the temperature is reduced to 50° C.; (2) acrylic acid monomer, 2-amino-3-butenoic acid, and azobisisobutyronitrile are added to (1), stirred and mixed evenly, triethylamine is added, and the temperature is increased to 70-80° C. for reflux reaction for a period of time until the isocyanate group content disappears, the reaction is terminated, and the silicone-modified polyurethane is obtained after purification.

[0010] Furthermore, the raw materials required for preparing the silicone-modified polyurethane include the following components: by weight, 8 to 16 parts of isophorone diisocyanate, 5 to 10 parts of polytetramethylene ether glycol, 5 to 10 parts of hydroxypropyl-terminated polydimethylsiloxane, 5 to 10 parts of acrylic acid monomer, 1 to 10 parts of 2-amino-3-butenoic acid, 0.5 to 1 part of azobisisobutyronitrile, and 0.5 to 1 part of triethylamine.

[0011] Furthermore, the acrylic monomer includes but is not limited to a combination of one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate.

[0012] Furthermore, the preparation method of the polydimethylsiloxane modified product is as follows: (1) tetrabutyl titanate, zirconium chloride, lanthanum chloride and neodymium chloride are added to deionized water, and a mixed solution is obtained by ultrasonic dispersion for 10 to 20 minutes; (2) the mixed solution is added to a hydrothermal reactor, and a hydrothermal reaction is carried out at 180 to 220° C. for 12 to 24 hours, the reaction is terminated, and the mixture is cooled naturally to room temperature, filtered and dried to obtain product A; (3) product A is placed in a muffle furnace, heated to 500 to 600° C. at a heating rate of 5 to 10° C. / min and fired for 4 to 8 hours, and after cooling naturally to room temperature, it is ground to 100 to 300 meshes and sieved to obtain product B; (4) product B and polydimethylsiloxane are added to anhydrous ethanol, ultrasonically dispersed for 10 to 20 minutes, heated to 50 to 60° C. and allowed to stand for 1 to 6 hours, and rotary evaporated to obtain a polydimethylsiloxane modified product.

[0013] Furthermore, the mass ratio of tetrabutyl titanate, zirconium chloride, lanthanum chloride and neodymium chloride is 1:(3~3.5):(0.2~0.5):(0.1~0.2).

[0014] Furthermore, the mass ratio of the product B, polydimethylsiloxane and anhydrous ethanol is 1:(0.2~0.3):10.

[0015] In the scheme, silicone-modified acrylate is added to the enhanced spray coating to improve the adhesion of the spray coating to the tempered glassware; silicone-modified polyurethane is also added, which can further improve the adhesion of the spray coating to the tempered glassware; polydimethylsiloxane silane modifier is further added, and the polydimethylsiloxane modifier contains metal elements such as titanium, zirconium, lanthanum, and neodymium, which can form a film layer on the surface of the tempered glassware, and the film layer can improve the stability of the tempered glassware during rapid cooling. In addition, silicone-modified polyurethane has good bonding with silicone-modified acrylate and polydimethylsiloxane modifier, which can make the film layer formed by the polydimethylsiloxane modifier more dense, uniform, and smooth, thereby better ensuring the strength of the tempered glassware.

[0016] Furthermore, the temperature rise treatment is divided into three steps, specifically: (1) heating to 70-80°C at a heating rate of 5-10°C / min, and keeping warm for 5-15 minutes; (2) then heating to 170-180°C at a heating rate of 2-4°C / min, and keeping warm for 10-30 minutes; (3) finally heating to 280-300°C at a heating rate of 1-2°C / min.

[0017] Furthermore, the heat preservation treatment is: heat preservation at 280-300° C. for 1-6 hours.

[0018] Furthermore, the cooling treatment is: spraying cooling gas onto the surface of the tempered glassware until the tempered glassware is cooled to 175-185°C, and then evenly spraying the enhanced spray coating and the cooling gas with the same parameters on the surface of the tempered glassware until the tempered glassware is cooled to 70-80°C.

[0019] Furthermore, the cooling gas is any one of liquid nitrogen or liquid carbon dioxide.

[0020] Furthermore, the spray parameters of the cooling gas are: if the thickness of the tempered glassware is ≤5mm, the spray speed is 30~60m / s and the spray pressure is 0.1~1.5MPa; if the thickness of the tempered glassware is >5mm, the spray speed is 80~140m / s and the spray pressure is 2~4MPa.

[0021] After the tempering treatment, the tempered glassware needs to be homogenized before the nickel sulfide inside it can be completely transformed from the α phase to the β phase, thereby completely eliminating the potential threat (self-explosion) brought by the nickel sulfide. The homogenization treatment is generally divided into a heating stage, a heat preservation stage, and a cooling stage. In order to shorten the homogenization treatment time as much as possible and improve the efficiency, the present invention makes corresponding arrangements for each stage. The heating stage is divided into three steps. Before 70~80℃, the temperature change in this stage will not have a significant impact on the tempered glass, so the temperature can be heated relatively quickly; then the heating rate is slowed down and controlled to a certain extent, which not only avoids excessive heating and causing large thermal stress in the tempered glass, but also greatly reduces the homogenization treatment time; finally, the temperature is slowly increased to 280~300℃ at a heating rate of 1~2℃ / min, which effectively weakens the threat of thermal stress to tempered glass and promotes the phase change of nickel sulfide inside the tempered glass at this temperature; at 280~300℃, after keeping warm for 1~6h, the "detonation treatment" of the tempered glass can be completed, and the α phase nickel sulfide is transformed into the β phase. Finally, the tempered glassware after insulation treatment is quickly cooled by cooling gas injection. The tempered glassware is suddenly cooled, and the inner and outer layers cool down at different speeds. The surface layer cools and shrinks rapidly, while the inner layer cools and shrinks slowly, forming a high-pressure state, compressing its surface, thereby enhancing the strength of the tempered glassware.

[0022] Compared with the prior art, the present invention has the following beneficial effects: 1. In the present invention, during the cooling stage of the homogenization treatment, the enhanced spraying liquid and the cooling gas are simultaneously sprayed on the tempered glassware, so that a dense, uniform and flat film layer is formed on the surface of the tempered glassware, thereby ensuring the stability of the tempered glassware and improving the strength of the tempered glassware; 2. In the present invention, the tempered glassware is homogenized and the temperature setting parameters of each treatment stage are comprehensively considered, which not only shortens the homogenization treatment time, but also ensures the anti-self-explosion ability of the tempered glassware, thereby ensuring the strength of the tempered glassware. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] It should be noted that the purchasers of all raw materials involved in the present invention include, without any special restrictions, illustratively: The model of organosilicon-modified acrylate is 8840, which was purchased from Shenzhen Haineng Chemical Co., Ltd.; Isophorone diisocyanate with a purity of 99%, hydroxypropyl-terminated polydimethylsiloxane with a purity of 99%, CAS number: 104780-66-7, zirconium chloride with a purity of 99%, and polydimethylsiloxane with a purity of 99%, were all purchased from Shanghai Jinjinle Industrial Co., Ltd.; Polytetramethylene glycol with a purity of 99.5%, azobisisobutyronitrile with a purity of 99%, tetrabutyl titanate with a purity of 99%, and lanthanum chloride with a purity of 99% were purchased from Hubei Jusheng Technology Co., Ltd.; Amino-3-butenoic acid with a purity of 99% was purchased from JACS-Zhengzhou Jacks Chemical Products Co., Ltd.; Neodymium chloride with a purity of 99.99% was purchased from Jining Tianyi New Materials Co., Ltd.; The waterborne polyurethane model was UH 2593-1, purchased from Hubei Kewode Chemical Co., Ltd.; In the following examples, each portion is 100 g.

[0025] Example 1: A preparation process of high-strength tempered glassware: S1: Prepare enhanced spray liquid: S11: Preparation of organosilicon-modified polyurethane: (1) Under nitrogen protection, add 15 parts of isophorone diisocyanate, 7 parts of polytetramethylene glycol, and 7 parts of hydroxypropyl-terminated polydimethylsiloxane to a reaction kettle, stir and heat to 100°C, reflux for a period of time, until the isocyanate content in the reaction system no longer changes, and then cool to 50°C; (2) Add 8 parts of acrylic acid monomer (methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate mixed in a mass ratio of 1:1:1:1), 5 parts of 2-amino-3-butenoic acid, and 0.8 parts of azobisisobutyronitrile to (1), stir and mix evenly, add 0.8 parts of triethylamine, and heat to 75°C for reflux for a period of time, until the isocyanate content disappears, terminate the reaction, and purify to obtain organosilicon-modified polyurethane; S12: Preparation of polydimethylsiloxane modified product: (1) Add 6 parts of tetrabutyl titanate, 19.8 parts of zirconium chloride, 2.4 parts of lanthanum chloride and 0.9 parts of neodymium chloride to 50 parts of deionized water, and disperse them by ultrasonication for 15 minutes to obtain a mixed solution; (2) Add the mixed solution to a hydrothermal reactor, and conduct a hydrothermal reaction at 190°C for 18 hours. After the reaction is terminated, the mixture is cooled to room temperature naturally, filtered and dried to obtain product A; (3) Product A is placed in a muffle furnace, heated to 580°C at a heating rate of 5°C / min and fired for 6 hours. After cooling to room temperature naturally, it is ground to 100 mesh and sieved to obtain product B; (4) Add 20 parts of product B and 5 parts of polydimethylsiloxane to 200 parts of anhydrous ethanol, disperse them by ultrasonication for 15 minutes, heat to 55°C and stand for 5 hours, and evaporate to obtain polydimethylsiloxane modified product; S13: adding 43 parts of organosilicon-modified acrylate, 24 parts of organosilicon-modified polyurethane, 18 parts of modified polydimethylsiloxane, 5 parts of ammonium sulfate, 8 parts of polyethylene glycol, 6 parts of melamine formaldehyde resin, and 50 parts of purified water into a stirring tank, mixing them evenly, to obtain an enhanced spraying liquid; S2: Homogenization: S21: placing the tempered glassware (3 mm thick) after the tempering treatment into a homogenizing furnace for heating treatment, specifically: (1) heating to 75°C at a heating rate of 8°C / min and keeping the temperature for 10 min; (2) then heating to 175°C at a heating rate of 3°C / min and keeping the temperature for 25 min; (3) finally heating to 290°C at a heating rate of 1.3°C / min; S22: After the heating treatment is completed, a heat preservation treatment is performed, specifically: heat preservation at 290° C. for 5 hours; S23: After the heat preservation treatment is completed, a cooling treatment is performed, specifically: liquid nitrogen is sprayed onto the surface of the tempered glassware until the tempered glassware is cooled to 180° C., and then the reinforcing spray coating and the cooling gas are evenly sprayed on the surface of the tempered glassware with the same parameters until the tempered glassware is cooled to 75° C., thereby obtaining a high-strength tempered glassware; wherein the spraying parameters of the liquid nitrogen are: a spraying speed of 50 m / s and a spraying pressure of 1 MPa.

[0026] Example 2: A preparation process of high-strength tempered glassware: S1: Prepare enhanced spray liquid: S11: Preparation of silicone-modified polyurethane: (1) Under nitrogen protection, add 15 parts of isophorone diisocyanate, 5 parts of polytetramethylene glycol, and 5 parts of hydroxypropyl-terminated polydimethylsiloxane to a reaction kettle, stir and heat to 100°C, reflux for a period of time, until the isocyanate group content in the reaction system no longer changes, and then cool to 50°C; (2) Add 5 parts of acrylic acid monomer (methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate mixed in a mass ratio of 1:1:1:1), 5 parts of 2-amino-3-butenoic acid, and 0.8 parts of azobisisobutyronitrile to (1), stir and mix evenly, add 0.8 parts of triethylamine, and heat to 75°C for reflux for a period of time, until the isocyanate group content disappears, terminate the reaction, and purify to obtain silicone-modified polyurethane; S12: Preparation of polydimethylsiloxane modified product: (1) Add 6 parts of tetrabutyl titanate, 18 parts of zirconium chloride, 1.2 parts of lanthanum chloride and 0.6 parts of neodymium chloride to 50 parts of deionized water, and disperse them by ultrasonication for 15 minutes to obtain a mixed solution; (2) Add the mixed solution to a hydrothermal reactor, and conduct a hydrothermal reaction at 190°C for 18 hours. After the reaction is terminated, the mixture is cooled naturally to room temperature, filtered and dried to obtain product A; (3) Product A is placed in a muffle furnace, heated to 580°C at a heating rate of 5°C / min and fired for 6 hours. After it is cooled naturally to room temperature, it is ground to 300 mesh and sieved to obtain product B; (4) Add 20 parts of product B and 4 parts of polydimethylsiloxane to 200 parts of anhydrous ethanol, disperse them by ultrasonication for 15 minutes, heat to 55°C and stand for 5 hours, and evaporate to obtain polydimethylsiloxane modified product; S13: adding 43 parts of organosilicon-modified acrylate, 24 parts of organosilicon-modified polyurethane, 18 parts of modified polydimethylsiloxane, 5 parts of ammonium sulfate, 8 parts of polyethylene glycol, 6 parts of melamine formaldehyde resin, and 50 parts of purified water into a stirring tank, mixing them evenly, to obtain an enhanced spraying liquid; S2: Homogenization: S21: placing the tempered glassware (3 mm thick) after the tempering treatment into a homogenizing furnace for heating treatment, specifically: (1) heating to 75°C at a heating rate of 10°C / min and keeping the temperature for 10 min; (2) then heating to 175°C at a heating rate of 4°C / min and keeping the temperature for 25 min; (3) finally heating to 290°C at a heating rate of 2°C / min; S22: After the heating treatment is completed, a heat preservation treatment is performed, specifically: heat preservation at 290° C. for 5 hours; S23: After the heat preservation treatment is completed, a cooling treatment is performed, specifically: liquid nitrogen is sprayed onto the surface of the tempered glassware until the tempered glassware is cooled to 180° C., and then the reinforcing spray coating and the cooling gas are evenly sprayed on the surface of the tempered glassware with the same parameters until the tempered glassware is cooled to 75° C., thereby obtaining a high-strength tempered glassware; wherein the spraying parameters of the liquid nitrogen are: a spraying speed of 50 m / s and a spraying pressure of 1 MPa.

[0027] Example 3: A preparation process of high-strength tempered glassware: S1: Prepare enhanced spray liquid: S11: Preparation of silicone-modified polyurethane: (1) Under nitrogen protection, add 15 parts of isophorone diisocyanate, 10 parts of polytetramethylene glycol, and 10 parts of hydroxypropyl-terminated polydimethylsiloxane to a reaction kettle, stir and heat to 100°C, reflux for a period of time, until the isocyanate group content in the reaction system no longer changes, and then cool to 50°C; (2) Add 10 parts of acrylic acid monomer (methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate mixed in a mass ratio of 1:1:1:1), 5 parts of 2-amino-3-butenoic acid, and 0.8 parts of azobisisobutyronitrile to (1), stir and mix evenly, add 0.8 parts of triethylamine, and heat to 75°C for reflux for a period of time, until the isocyanate group content disappears, terminate the reaction, and purify to obtain silicone-modified polyurethane; S12: Preparation of polydimethylsiloxane modified product: (1) Add 6 parts of tetrabutyl titanate, 21 parts of zirconium chloride, 3 parts of lanthanum chloride and 1.2 parts of neodymium chloride to 50 parts of deionized water, and disperse by ultrasonication for 15 minutes to obtain a mixed solution; (2) Add the mixed solution to a hydrothermal reactor, and conduct hydrothermal reaction at 190°C for 18 hours. After the reaction is terminated, the mixture is cooled to room temperature naturally, filtered and dried to obtain product A; (3) Product A is placed in a muffle furnace, heated to 580°C at a heating rate of 5°C / min and fired for 6 hours. After cooling to room temperature naturally, it is ground to 100 mesh and sieved to obtain product B; (4) Add 20 parts of product B and 6 parts of polydimethylsiloxane to 200 parts of anhydrous ethanol, disperse by ultrasonication for 15 minutes, heat to 55°C and stand for 5 hours, and evaporate to obtain polydimethylsiloxane modified product; S13: adding 43 parts of organosilicon-modified acrylate, 24 parts of organosilicon-modified polyurethane, 18 parts of modified polydimethylsiloxane, 5 parts of ammonium sulfate, 8 parts of polyethylene glycol, 6 parts of melamine formaldehyde resin, and 50 parts of purified water into a stirring tank, mixing them evenly, to obtain an enhanced spraying liquid; S2: Homogenization: S21: placing the tempered glassware (3 mm thick) after the tempering treatment into a homogenizing furnace for heating treatment, specifically: (1) heating to 75°C at a heating rate of 5°C / min and keeping the temperature for 10 min; (2) then heating to 175°C at a heating rate of 2°C / min and keeping the temperature for 25 min; (3) finally heating to 290°C at a heating rate of 1°C / min; S22: After the heating treatment is completed, a heat preservation treatment is performed, specifically: heat preservation at 290° C. for 5 hours; S23: After the heat preservation treatment is completed, a cooling treatment is performed, specifically: liquid nitrogen is sprayed onto the surface of the tempered glassware until the tempered glassware is cooled to 180° C., and then the reinforcing spray coating and the cooling gas are evenly sprayed on the surface of the tempered glassware with the same parameters until the tempered glassware is cooled to 75° C., thereby obtaining a high-strength tempered glassware; wherein the spraying parameters of the liquid nitrogen are: a spraying speed of 50 m / s and a spraying pressure of 1 MPa.

[0028] Based on Example 1, control experiments are set up below, specifically comparative examples 1 to 4, as described below: Comparative Example 1: Comparative Example 1 is based on Example 1, with the following modifications: no silicone-modified polyurethane is added, and water-based polyurethane is used instead, and the rest remains unchanged, specifically: A preparation process of high-strength tempered glassware: S1: Prepare enhanced spray liquid: S11: Preparation of polydimethylsiloxane modified product: (1) Add 6 parts of tetrabutyl titanate, 19.8 parts of zirconium chloride, 2.4 parts of lanthanum chloride and 0.9 parts of neodymium chloride to 50 parts of deionized water, and disperse them by ultrasonication for 15 minutes to obtain a mixed solution; (2) Add the mixed solution to a hydrothermal reactor, and conduct a hydrothermal reaction at 190°C for 18 hours. After the reaction is terminated, the mixture is cooled naturally to room temperature, filtered and dried to obtain product A; (3) Product A is placed in a muffle furnace, heated to 580°C at a heating rate of 5°C / min and fired for 6 hours. After it is cooled naturally to room temperature, it is ground to 100 mesh and sieved to obtain product B; (4) Add 20 parts of product B and 5 parts of polydimethylsiloxane to 200 parts of anhydrous ethanol, disperse them by ultrasonication for 15 minutes, heat to 55°C and stand for 5 hours, and evaporate to obtain polydimethylsiloxane modified product; S12: 43 parts of organosilicon-modified acrylate, 24 parts of waterborne polyurethane, 18 parts of modified polydimethylsiloxane, 5 parts of ammonium sulfate, 8 parts of polyethylene glycol, 6 parts of melamine formaldehyde resin, and 50 parts of purified water are added into a stirring tank and mixed evenly to obtain an enhanced spraying liquid; S2: Homogenization: S21: placing the tempered glassware (3 mm thick) after the tempering treatment into a homogenizing furnace for heating treatment, specifically: (1) heating to 75°C at a heating rate of 8°C / min and keeping the temperature for 10 min; (2) then heating to 175°C at a heating rate of 3°C / min and keeping the temperature for 25 min; (3) finally heating to 290°C at a heating rate of 1.3°C / min; S22: After the heating treatment is completed, a heat preservation treatment is performed, specifically: heat preservation at 290° C. for 5 hours; S23: After the heat preservation treatment is completed, a cooling treatment is performed, specifically: liquid nitrogen is sprayed onto the surface of the tempered glassware until the tempered glassware is cooled to 180° C., and then the reinforcing spray coating and the cooling gas are evenly sprayed on the surface of the tempered glassware with the same parameters until the tempered glassware is cooled to 75° C., thereby obtaining a high-strength tempered glassware; wherein the spraying parameters of the liquid nitrogen are: a spraying speed of 50 m / s and a spraying pressure of 1 MPa.

[0029] Comparative Example 2: Comparative Example 2 is based on Example 1, with the following adjustments: no polydimethylsiloxane modifier is added, and polydimethylsiloxane is used instead, and other processes remain unchanged, specifically: A preparation process of high-strength tempered glassware: S1: Prepare enhanced spray liquid: S11: Preparation of organosilicon-modified polyurethane: (1) Under nitrogen protection, add 15 parts of isophorone diisocyanate, 7 parts of polytetramethylene glycol, and 7 parts of hydroxypropyl-terminated polydimethylsiloxane to a reaction kettle, stir and heat to 100°C, reflux for a period of time, until the isocyanate content in the reaction system no longer changes, and then cool to 50°C; (2) Add 8 parts of acrylic acid monomer (methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate mixed in a mass ratio of 1:1:1:1), 5 parts of 2-amino-3-butenoic acid, and 0.8 parts of azobisisobutyronitrile to (1), stir and mix evenly, add 0.8 parts of triethylamine, and heat to 75°C for reflux for a period of time, until the isocyanate content disappears, terminate the reaction, and purify to obtain organosilicon-modified polyurethane; S12: adding 43 parts of organosilicon-modified acrylate, 24 parts of organosilicon-modified polyurethane, 18 parts of polydimethylsiloxane, 5 parts of ammonium sulfate, 8 parts of polyethylene glycol, 6 parts of melamine formaldehyde resin, and 50 parts of purified water into a stirring tank, and mixing them evenly to obtain an enhanced spraying liquid; S2: Homogenization: S21: placing the tempered glassware (3 mm thick) after the tempering treatment into a homogenizing furnace for heating treatment, specifically: (1) heating to 75°C at a heating rate of 8°C / min and keeping the temperature for 10 min; (2) then heating to 175°C at a heating rate of 3°C / min and keeping the temperature for 25 min; (3) finally heating to 290°C at a heating rate of 1.3°C / min; S22: After the heating treatment is completed, a heat preservation treatment is performed, specifically: heat preservation at 290° C. for 5 hours; S23: After the heat preservation treatment is completed, a cooling treatment is performed, specifically: liquid nitrogen is sprayed onto the surface of the tempered glassware until the tempered glassware is cooled to 180° C., and then the reinforcing spray coating and the cooling gas are evenly sprayed on the surface of the tempered glassware with the same parameters until the tempered glassware is cooled to 75° C., thereby obtaining a high-strength tempered glassware; wherein the spraying parameters of the liquid nitrogen are: a spraying speed of 50 m / s and a spraying pressure of 1 MPa.

[0030] Comparative Example 3: Comparative Example 3 is based on Example 1, with the following modifications: no silicone-modified polyurethane and polydimethylsiloxane-modified product are added, and aqueous polyurethane and polydimethylsiloxane are used instead, respectively, and other processes remain unchanged, specifically: A preparation process of high-strength tempered glassware: S1: Prepare enhanced spray liquid: S11: adding 43 parts of organosilicon-modified acrylate, 24 parts of waterborne polyurethane, 18 parts of polydimethylsiloxane, 5 parts of ammonium sulfate, 8 parts of polyethylene glycol, 6 parts of melamine formaldehyde resin, and 50 parts of purified water into a stirring tank, and mixing them evenly to obtain an enhanced spraying liquid; S2: Homogenization: S21: placing the tempered glassware (3 mm thick) after the tempering treatment into a homogenizing furnace for heating treatment, specifically: (1) heating to 75°C at a heating rate of 8°C / min and keeping the temperature for 10 min; (2) then heating to 175°C at a heating rate of 3°C / min and keeping the temperature for 25 min; (3) finally heating to 290°C at a heating rate of 1.3°C / min; S22: After the heating treatment is completed, a heat preservation treatment is performed, specifically: heat preservation at 290° C. for 5 hours; S23: After the heat preservation treatment is completed, a cooling treatment is performed, specifically: liquid nitrogen is sprayed onto the surface of the tempered glassware until the tempered glassware is cooled to 180° C., and then the reinforcing spray coating and the cooling gas are evenly sprayed on the surface of the tempered glassware with the same parameters until the tempered glassware is cooled to 75° C., thereby obtaining a high-strength tempered glassware; wherein the spraying parameters of the liquid nitrogen are: a spraying speed of 50 m / s and a spraying pressure of 1 MPa.

[0031] Comparative Example 4: Comparative Example 4 is based on Example 1, with the following adjustments: no enhanced spray coating is sprayed during the cooling process, and other processes remain unchanged, specifically: A preparation process of high-strength tempered glassware: S1: Homogenization: S21: placing the tempered glassware (3 mm thick) after the tempering treatment into a homogenizing furnace for heating treatment, specifically: (1) heating to 75°C at a heating rate of 8°C / min and keeping the temperature for 10 min; (2) then heating to 175°C at a heating rate of 3°C / min and keeping the temperature for 25 min; (3) finally heating to 290°C at a heating rate of 1.3°C / min; S22: After the heating treatment is completed, a heat preservation treatment is performed, specifically: heat preservation at 290° C. for 5 hours; S23: After the heat preservation treatment is completed, a cooling treatment is performed, specifically: liquid nitrogen is sprayed onto the surface of the tempered glassware until the tempered glassware is cooled to 75° C., thereby obtaining a high-strength tempered glassware; wherein the spraying parameters of the liquid nitrogen are: a spraying speed of 50 m / s and a spraying pressure of 1 MPa.

[0032] Performance test: The physical and chemical performance tests were conducted on the high-strength tempered glassware prepared in Examples 1 to 3 and Comparative Examples 1 to 4, and ordinary tempered glassware sold on the market was selected for comparison. The specific test results are shown in Table 1 below: Table 1

[0033] Result analysis: It can be seen from Table 1 above that the compressive stress of the high-strength tempered glassware prepared in the embodiment of the present invention can reach more than 850 MPa, and the Mohs hardness can reach up to 6.8; compared with ordinary tempered glassware purchased on the market, it has higher strength.

[0034] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A process for preparing high-strength tempered glassware, characterized in that: The following steps are involved: S1: Evenly mix organosilicon-modified acrylate, organosilicon-modified polyurethane, polydimethylsiloxane modification, ammonium sulfate, polyethylene glycol, melamine formaldehyde resin, and deionized water to obtain an enhanced spraying liquid; The enhanced spraying liquid comprises the following components: by weight: 40-50 parts of organosilicon-modified acrylate, 15-25 parts of organosilicon-modified polyurethane, 10-20 parts of modified polydimethylsiloxane, 3-6 parts of ammonium sulfate, 5-10 parts of polyethylene glycol, 4-8 parts of melamine formaldehyde resin, and 50 parts of deionized water; S2: homogenize the tempered glassware; S21: placing the tempered glassware into a homogenizing furnace for heating; S22: After the heating process is completed, a heat preservation process is performed; S23: After the heat preservation treatment is completed, a cooling treatment is performed to obtain a high-strength tempered glass container.

2. The process for preparing a high-strength tempered glass container according to claim 1, characterized in that: The preparation method of the organosilicon-modified polyurethane is as follows: (1) under nitrogen protection, isophorone diisocyanate, polytetramethylene glycol, and hydroxypropyl-terminated polydimethylsiloxane are added to a reaction kettle, stirred and heated to 70-150° C. for reflux reaction for a period of time until the isocyanate group content in the reaction system no longer changes, and then the temperature is reduced to 50° C.; (2) acrylic acid monomer, 2-amino-3-butenoic acid, and azobisisobutyronitrile are added to (1), stirred and mixed evenly, triethylamine is added, and the temperature is increased to 70-80° C. for reflux reaction for a period of time until the isocyanate group content disappears, the reaction is terminated, and the organosilicon-modified polyurethane is obtained after purification; The raw materials required for preparing the silicone-modified polyurethane include the following components: by weight, 8 to 16 parts of isophorone diisocyanate, 5 to 10 parts of polytetramethylene ether glycol, 5 to 10 parts of hydroxypropyl-terminated polydimethylsiloxane, 5 to 10 parts of acrylic acid monomer, 1 to 10 parts of 2-amino-3-butenoic acid, 0.5 to 1 part of azobisisobutyronitrile, and 0.5 to 1 part of triethylamine.

3. The process for preparing a high-strength tempered glass container according to claim 2, characterized in that: The acrylic monomer includes one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate and ethyl acrylate.

4. The process for preparing a high-strength tempered glass container according to claim 1, characterized in that: The preparation method of the polydimethylsiloxane modified product is as follows: (1) adding tetrabutyl titanate, zirconium chloride, lanthanum chloride and neodymium chloride to deionized water, and ultrasonically dispersing for 10 to 20 minutes to obtain a mixed solution; (2) adding the mixed solution to a hydrothermal reactor, hydrothermally reacting at 180 to 220° C. for 12 to 24 hours, terminating the reaction, and allowing it to cool naturally to room temperature, filtering and drying to obtain product A; (3) placing product A in a muffle furnace, heating it to 500 to 600° C. at a heating rate of 5 to 10° C. / min and firing it for 4 to 8 hours, and after allowing it to cool naturally to room temperature, grinding it to 100 to 300 meshes, sieving it, and obtaining product B; (4) adding product B and polydimethylsiloxane to anhydrous ethanol, ultrasonically dispersing it for 10 to 20 minutes, heating it to 50 to 60° C. and standing it for 1 to 6 hours, and rotary evaporating it to obtain a polydimethylsiloxane modified product; Among them, the mass ratio of tetrabutyl titanate, zirconium chloride, lanthanum chloride and neodymium chloride is 1:(3~3.5):(0.2~0.5):(0.1~0.2); the mass ratio of product B, polydimethylsiloxane and anhydrous ethanol is 1:(0.2~0.3):

10.

5. The process for preparing a high-strength tempered glass container according to claim 1, characterized in that: The heating treatment is divided into three steps, specifically: (1) heating to 70-80°C at a heating rate of 5-10°C / min, and keeping warm for 5-15 minutes; (2) then heating to 170-180°C at a heating rate of 2-4°C / min, and keeping warm for 10-30 minutes; (3) finally heating to 280-300°C at a heating rate of 1-2°C / min.

6. The process for preparing a high-strength tempered glass container according to claim 1, characterized in that: The heat preservation treatment is: heat preservation at 280-300° C. for 1-6 hours.

7. The process for preparing a high-strength tempered glass container according to claim 1, characterized in that: The cooling treatment is as follows: spraying cooling gas onto the surface of the tempered glassware until the tempered glassware is cooled to 175-185°C, and then evenly spraying the enhanced spray coating together with the cooling gas onto the surface of the tempered glassware until the tempered glassware is cooled to 70-80°C.

8. The process for preparing a high-strength tempered glass container according to claim 7, characterized in that: The cooling gas is any one of liquid nitrogen or liquid carbon dioxide; the spray parameters of the cooling gas are: if the thickness of the tempered glassware is ≤5mm, the spray speed is 30~60m / s and the spray pressure is 0.1~1.5MPa; if the thickness of the tempered glassware is greater than 5mm, the spray speed is 80~140m / s and the spray pressure is 2~4MPa.

9. The high-strength tempered glassware prepared by the preparation process according to any one of claims 1 to 8.

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