Method for preparing glass from natural resin acid resource
The natural resin acid glass material prepared by high-temperature melt annealing process solves the bottleneck of sustainable development of existing glass technology and the humidity sensitivity problem of room temperature phosphorescent materials. It achieves transparency, reshaping and hydrophobic photoactivated room temperature phosphorescence performance, and is suitable for a variety of application scenarios.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-27
- Publication Date
- 2026-03-10
AI Technical Summary
Existing glass technologies have shortcomings in terms of cost, processing complexity, biocompatibility, natural decomposition rate, and closed-loop recycling. Furthermore, organic room temperature phosphorescent materials are susceptible to phosphorescence quenching due to humidity or water, and photoluminescent materials lack plasticity and are not reusable.
Glass is prepared by using natural resin acid compounds through a high-temperature melt annealing process. The material has good transparency and hydrophobicity, can exhibit photoactivated room temperature phosphorescence properties in air and water, and can be repeatedly shaped.
The prepared glass material has good hydrophobicity and reusability, which solves the problem of room temperature phosphorescent materials being quenched when exposed to water. It achieves transparent and reproducible photoactivated room temperature phosphorescence performance, and is suitable for underwater phosphorescence operations, intelligent anti-counterfeiting and 3D/4D phosphorescence fields.
Smart Images
Figure CN121628620A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of bio-based glass preparation technology, and in particular to a method for preparing photoactivated room temperature phosphorescent glass from natural resin acid resources. Background Technology
[0002] Glass is a crucial component of advanced materials systems, and various types of glass, including inorganic and organic glass, have been developed. However, current glass technologies suffer from significant shortcomings in terms of cost, processing complexity, biocompatibility, natural decomposition rates, and closed-loop recycling, hindering sustainable development. This underscores the urgent need to develop low-cost, simple-to-process, fully biodegradable, and biorecyclable glass systems to minimize environmental impacts while supporting sustainable mitigation of ecological and social impacts.
[0003] Photoactivated room-temperature phosphorescent materials have wide applications in optical printing, 3D displays, and information storage. Generally, before light irradiation, these materials exhibit negligible or no room-temperature phosphorescence. After exposing the material to a light source for a certain period, long-lived room-temperature phosphorescence emission can be observed. Common photoactivated room-temperature phosphorescent polymer composites are often prepared by confining chromophore molecules within a polymer matrix, a complex process requiring multiple steps. Furthermore, many of these phosphorescent composites are frequently affected by external humidity or water, leading to phosphorescence quenching. In addition, the materials used are typically derived from non-renewable fossil resources.
[0004] Natural resin acids are one of my country's important forest resources. Due to their abundance and high renewability, their processed products are widely studied and applied. Currently, based on their structural characteristics, such as conjugated systems and the steric hindrance structure of tricyclic phenanthrene molecules, research on their derivatives in photoluminescence has been gradually carried out. However, research on their optical properties mainly focuses on fluorescence emission, while research on the creation of organophosphorus light-emitting materials is still in its early stages. Summary of the Invention
[0005] To address the aforementioned problems, this invention provides a method for preparing glass from natural resin acid resources. This invention utilizes resin acid compounds as raw materials and prepares glass materials through a simple melt-annealing process. The resulting glass exhibits good transparency and displays photoactivated room-temperature phosphorescence emission in air and water. Furthermore, the glass possesses good plasticity, can be easily crushed, and can be reshaped using the same method, thus exhibiting reversible shaping characteristics. This research, through a simple melt-annealing process, enables the direct molding of transparent glass from natural elemental molecules, while simultaneously solving the key scientific problem of water-induced quenching of phosphorescence in room-temperature phosphorescent materials.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] This invention provides a method for preparing glass from natural resin acid resources, comprising the following steps: melting natural resin acid, annealing and cooling to obtain glass;
[0008] The natural resin acid resources include one or more of dehydrogenated rosin, hydrogenated rosin, and rosin.
[0009] Preferably, when the natural resin acid resource is dehydrogenated rosin, the melting temperature of the dehydrogenated rosin is 175-350°C and the melting time is 1-25 min.
[0010] Preferably, when the natural resin acid resource is hydrogenated rosin, the melting temperature of the hydrogenated rosin is 160-300°C and the melting time is 1-25 min.
[0011] Preferably, when the natural resin acid resource is rosin, the melting temperature of the rosin is 110-260°C and the melting time is 1-20 min.
[0012] The beneficial effects of this invention are:
[0013] This invention addresses the serious shortcomings of current glass manufacturing technologies in terms of cost, processing complexity, biocompatibility, natural decomposition rate, and closed-loop recycling, which hinder the sustainable development of glass production. It also addresses the problems of organic room-temperature phosphorescent materials often experiencing phosphorescence quenching due to the loss of triplet exciton vibrations in the luminescent clusters caused by humidity or water exposure, as well as the insufficient plasticity and non-reusability of photoluminescent materials. Utilizing the high-temperature melting and low-temperature solidification characteristics of natural resin acid compounds, a transparent, glassy, hydrophobic, photoactivated organic phosphorescent glass material has been developed. This glass material exhibits extremely high plasticity, good hydrophobicity, reusability, and repeated shaping advantages. When the glass is thin (<1 mm), due to the presence of triplet oxygen in the air... 3 The influence of O2 causes its initial phosphorescence to be weak or quenched. When irradiated with a 365nm light source, the triplet oxygen in the air (O2) is affected, resulting in weak or quenched initial phosphorescence. 3O2 is consumed, and the material's room-temperature phosphorescence is activated by the excited triplet state of excited electrons in the resin acid compounds. The phosphorescence intensity and lifetime increase with prolonged UV irradiation, reaching a maximum before gradually decreasing. This is because the UV irradiation process increases the material's temperature, thus reducing its phosphorescence intensity. Without single-source excitation, the phosphorescence effect weakens and eventually quenches after being placed in air due to O2 redispersing into the material. With increasing glass thickness (>1 mm), O2 cannot completely diffuse into the glass interior. When irradiated with a 365 nm light source, significant room-temperature phosphorescence can be observed. The thicker the material, the higher the room-temperature phosphorescence intensity, the longer the lifetime, and the longer the afterglow time. This photoactivated room-temperature phosphorescent glass can be repeatedly remolded using a high-temperature melting and annealing process. After molding, the glass material still exhibits good photoactivated room-temperature phosphorescence properties. Furthermore, the glass material has a contact angle exceeding 90° and good hydrophobicity; placing it in water also results in photoactivated room-temperature phosphorescence emission.
[0014] The beneficial effects of this invention are:
[0015] (1) Natural resin acid compounds can be melted at high temperature and then annealed to room temperature to form transparent glass-like materials of different shapes. The material has the characteristic of being reshapeable, which solves the key problem of the current glass materials not being reshapeable and breaks through the limitation that natural biomass and elemental compounds cannot be directly used to prepare glass-like materials.
[0016] (2) The material has good hydrophobicity and has photoactivated room temperature phosphorescence properties in air and water. Moreover, the long-term immersion of the glass material in water will not affect its photoactivated room temperature phosphorescence performance. This material solves the key problem of phosphorescence quenching of current room temperature phosphorescent materials when exposed to water.
[0017] (3) The preparation of this photoactivated room temperature phosphorescent glass material does not involve other compounds, the process is simple, green and environmentally friendly, and the raw material utilization rate and glass product yield are both 100%. Utilizing the hydrophobicity and photoactivated room temperature phosphorescence emission properties of this material, it has great application potential in underwater phosphorescence operations, intelligent anti-counterfeiting and 3D and 4D phosphorescence fields. Attached Figure Description
[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the embodiments will be briefly described below.
[0019] Figure 1 The images show the UV-Vis transmission of the transparent glass prepared in Example 6 and a real-world image of the glass placed on a plant. This glass can block ultraviolet light <400nm and has good transmittance for visible light.
[0020] Figure 2 Phosphorescence emission spectra of the transparent glass prepared in Example 6 at different times of light activation in air and water samples;
[0021] Figure 3 This is a hydrophobic angle test diagram of the glass prepared in Example 6; the test showed that its contact angle could reach 108°, confirming that the material has good hydrophobicity;
[0022] Figure 4 The images show the room temperature phosphorescence emission spectra of glasses with different thicknesses prepared in Example 6. The phosphorescence emission intensity of the glass material gradually increases with the increase of glass thickness.
[0023] Figure 5 The glass prepared in Example 10 exhibits yellow-green phosphorescence emission after being activated by 365nm light irradiation and the light source is turned off, confirming that the glass material has photoactivated phosphorescence emission performance.
[0024] Figure 6 These are repeated shaping photographs of the phosphorescent glass material prepared in Example 6; the glass material can be repeatedly processed into 3D glass-like objects, and emits yellow-green phosphorescence after being activated by 365nm light and after the light source is turned off. Detailed Implementation
[0025] This invention provides a method for preparing glass from natural resin acid resources, comprising the following steps: melting natural resin acid, annealing and cooling to obtain glass; wherein the natural resin acid resources include one or more of dehydrogenated rosin, hydrogenated rosin and rosin.
[0026] In this invention, the structure of the dehydrogenated rosin is as follows:
[0027]
[0028] In this invention, the structure of the hydrogenated rosin is as follows:
[0029]
[0030] In this invention, the structure of the rosin is as follows:
[0031]
[0032] In this invention, when the natural resin acid resource is preferably dehydrogenated rosin, the melting temperature of the dehydrogenated rosin is preferably 175–350°C, and the melting time is preferably 1–25 min. In this invention, when the natural resin acid resource is preferably hydrogenated rosin, the melting temperature of the hydrogenated rosin is preferably 160–300°C, and the melting time is preferably 1–25 min. When the natural resin acid resource is preferably rosin, the melting temperature of the rosin is preferably 110–260°C, and the melting time is preferably 1–20 min. To further illustrate this invention, the following detailed description is provided in conjunction with embodiments, but these should not be construed as limiting the scope of protection of this invention.
[0033] Example 1
[0034] 5g of dehydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 175℃ for 25 minutes until completely melted. The melt was then poured into a mold and annealed before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence.
[0035] Example 2
[0036] 4g of dehydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 190℃ for 20 minutes until completely melted. The melt was then poured into a mold and allowed to anneal before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence.
[0037] Example 3
[0038] 4.5g of dehydrorosin was added to a flat-bottomed flask and reacted in an oil bath at 240℃ for 15 minutes until completely melted. The melt was then poured into a mold and allowed to cool completely to room temperature to obtain a transparent glass. This glass, when excited by a 365nm light source, exhibits yellow-green light activating room-temperature phosphorescence emission.
[0039] Example 4
[0040] 6g of dehydrogenated rosin was added to a flat-bottomed flask and reacted in an oil bath at 300℃ for 5 minutes until completely melted. The melt was then poured into a mold and annealed before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence emission.
[0041] Example 5
[0042] 2g of dehydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 175℃ for 15 minutes until completely melted. The melt was then poured into a mold and annealed before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence emission.
[0043] Example 6
[0044] 1g of dehydrorosin was added to a flat-bottomed flask and heated in an oil bath at 180℃ for 5 minutes until completely melted. The melt was then poured into a mold and allowed to anneal before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence emission.
[0045] Example 7
[0046] 1g of dehydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 350℃ for 1 minute until completely melted. The melt was then poured into a mold and allowed to anneal before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence emission.
[0047] Example 8
[0048] 5g of hydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 160℃ for 25 minutes until completely melted. The melt was then poured into a mold and annealed before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence.
[0049] Example 9
[0050] 8g of hydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 260℃ for 18 minutes until completely melted. The melt was then poured into a mold and allowed to anneal before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light activating room-temperature phosphorescence emission.
[0051] Example 10
[0052] 0.5g of hydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 160℃ for 5 minutes until completely melted. The melt was then poured into a mold and allowed to anneal before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence.
[0053] Example 11
[0054] 1g of hydrogenated rosin was added to a flat-bottomed flask and heated in an oil bath at 300℃ for 1 minute until completely melted. The melt was then poured into a mold and allowed to anneal before being completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence.
[0055] Example 12
[0056] Add 2g of rosin to a flat-bottomed flask, heat it in an oil bath at 110℃ for 10 minutes until it is completely melted, pour it into a mold, and after annealing, cool it completely to room temperature to obtain transparent glass.
[0057] Example 13
[0058] Add 3g of rosin to a flat-bottomed flask, heat it in an oil bath at 190℃ for 8 minutes until it is completely melted, pour it into a mold, and after annealing, cool it completely to room temperature to obtain transparent glass.
[0059] Example 14
[0060] Add 7g of rosin to a flat-bottomed flask, heat it in an oil bath at 200℃ for 20 minutes until it is completely melted, pour it into a mold, and after annealing, cool it completely to room temperature to obtain transparent glass.
[0061] Example 15
[0062] Add 1g of rosin to a flat-bottomed flask, heat it in an oil bath at 260℃ for 1 minute until it is completely melted, pour it into a mold, and after annealing, cool it completely to room temperature to obtain transparent glass.
[0063] Example 16
[0064] 1.5g of dehydrogenated rosin was heated to 200℃ on a hot plate for 8 minutes until completely melted, then poured into a mold. After annealing, it was completely cooled to room temperature to obtain transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light activating room-temperature phosphorescence emission.
[0065] Example 17
[0066] 1.5g of dehydrogenated rosin was heated in a 250℃ high-temperature sintering furnace for 1 minute until completely melted, then poured into a mold. After annealing, it was completely cooled to room temperature to obtain transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light activating room-temperature phosphorescence emission.
[0067] Example 18
[0068] 1.5g of dehydrogenated rosin was heated to complete melting in a tube furnace at 260℃ with argon gas for 1 minute. After annealing, it was completely cooled to room temperature to obtain a transparent glass. When excited by a 365nm light source, the glass exhibited yellow-green light and activated room-temperature phosphorescence emission.
[0069] Figure 1 UV-Vis transmittance image of the transparent glass prepared in Example 6 and a photograph of the glass placed on a plant. As can be seen from the images, the glass can block ultraviolet light <400nm and has good transmittance for visible light.
[0070] Figure 2 The phosphorescence emission spectra of the transparent glass prepared in Example 6 at different times of light activation in air and water samples show that the phosphorescence emission intensity increases with the extension of light exposure time, confirming that the glass material has photoactivated phosphorescence emission properties.
[0071] Figure 3 This is a hydrophobic angle test diagram of the glass prepared in Example 6. The test showed that its contact angle reached 108°, confirming that the material has good hydrophobicity.
[0072] Figure 4 The following are the room temperature phosphorescence emission spectra of glass with different thicknesses prepared in Example 6. As can be seen from the figure, the phosphorescence emission intensity of the glass material gradually increases with the increase of glass thickness.
[0073] Figure 5 The glass prepared in Example 10 exhibits yellow-green phosphorescence emission after being activated by 365nm light irradiation and the light source is turned off, confirming that the glass material has photoactivated phosphorescence emission performance.
[0074] Figure 6 These are photographs of the phosphorescent glass material prepared in Example 6, showing repeated shaping. As can be seen from the figures, this glass material can be repeatedly processed into 3D glass-like objects, and emits yellow-green phosphorescence after being activated by 365nm light and after the light source is turned off.
[0075] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.
Claims
1. A method for producing glass from natural resin acid resources, characterized by, The method comprises the following steps: melting natural resin acid, and obtaining glass after annealing and cooling; the natural resin acid resource comprises one or more of dehydrogenated rosin, hydrogenated rosin and rosin.
2. The method of claim 1, wherein, when the natural resin acid resource is dehydrogenated rosin, the melting temperature of the dehydrogenated rosin is 175-350℃, and the time is 1-25 min.
3. The method of claim 1, wherein, when the natural resin acid resource is hydrogenated rosin, the melting temperature of the hydrogenated rosin is 160-300℃, and the time is 1-25 min.
4. The method of claim 1, wherein, when the natural resin acid resource is rosin, the melting temperature of the rosin is 110-260℃, and the time is 1-20 min.