Ultraviolet light double-effect self-repairing type polymer fragrance releasing material and preparation method thereof

Abstract

The invention discloses an ultraviolet light double-effect self-repairing type polymer fragrance releasing material and a preparation method thereof. The ultraviolet light double-effect self-repairing type polymer fragrance releasing material is prepared by mixing a film forming base material A and an active component B, the film-forming base material A comprises the following components in parts by mass: 45-55 parts of acrylic resin, 4-6 parts of hollow glass beads, 4-6 parts of dextrin, 6-8 parts of a coalescing agent, 10-14 parts of epoxy resin and 8-12 parts of ionized water; the active component B is prepared from the following components in parts by mass: 8 to 12 parts of cinnamyl aldehyde, 8 to 12 parts of methyl aminobenzoate, 2 to 3 parts of allicin, 2 to 4 parts of an ultraviolet light absorber, 2 to 4 parts of an ultraviolet light isolating agent and 18 to 22 parts of ionized water. The high-molecular fragrance-releasing material prepared according to the ratio can resist ultraviolet erosion, can dynamically self-repair after tiny cracks appear on the surface, and can keep stability and relatively strong adhesive force in different environments of high and low temperatures, so that a long-term stable bird repelling effect is realized.

Description

Technical Field

[0001] This invention relates to a polymeric fragrance-releasing material and its preparation method, specifically a self-healing polymeric fragrance-releasing material with dual ultraviolet light effects and its preparation method. Background Technology

[0002] Slow-release technology for fragrances and flavorings has wide applications in daily chemicals, textiles, smart homes, and ecological security (such as bird repellency and insect control). To achieve sustained fragrance release and improve the stability of active ingredients, using polymer materials as carriers to encapsulate, adsorb, or chemically bind fragrances has become the mainstream technology in the industry. With the continuous expansion of application scenarios, the market is placing higher demands on the functionality of fragrance-releasing materials. For example, in agriculture, forestry, power systems, and airport security, using fragrance-releasing bird-repelling materials to replace traditional physical defenses (such as scarecrows and bird nets) or sensory interferences (such as strong light and sound waves) has become a convenient, environmentally friendly, and large-scale application research hotspot. This technology, which achieves active defense by releasing repulsive fragrances, greatly solves the bottleneck problems of high cost, easy adaptation, and difficulty in economical and efficient application of traditional bird-repelling methods.

[0003] Due to the advantages of the aforementioned bird-repelling materials, they are gradually replacing traditional physical and acoustic bird repellents, becoming the mainstream application in the current bird repelling technology field. Patent CN120660703A discloses a bird repellent based on thiocyanate, which extends the release time and maintains a high bird-repelling rate even under high temperature and rain conditions. This solves the problems of short-lasting effect and poor weather resistance of existing bird repellents. Patent CN121128735A utilizes the electrostatic interaction between positively charged modified β-cyclodextrin and negatively charged protein nanoparticles to construct a stable and dense "molecular inclusion + physical barrier" dual sustained-release structure, preparing a highly efficient, long-lasting, and extremely weather-resistant bird repellent product. While the aforementioned existing technologies have made some progress in extending the release time of bird repellents and improving weather resistance, they are still insufficient in addressing the failure issues caused by long-term strong ultraviolet radiation and mechanical damage (such as rain). Specifically: First, to ensure the effectiveness of odor release, bird repellent materials need to be coated onto the surface of a box or panel and placed directly in an open air environment (placing the bird repellent material inside a box or container greatly reduces its effectiveness). This prolonged exposure to strong ultraviolet radiation easily leads to aging of the coating substrate and degradation of active ingredients. Furthermore, existing materials often struggle to withstand drastic temperature differences between extreme cold and heat, making them prone to brittleness or softening and peeling off. Second, existing bird repellent materials lack self-repair capabilities after mechanical damage caused by wind, rain, or other impacts. Once micro-cracks appear on the surface of the material, the internal active ingredients evaporate rapidly, resulting in a sharp decrease in bird repellency.

[0004] In summary, the development of a long-lasting fragrance-releasing material that can resist ultraviolet radiation, possess dynamic self-healing capabilities, maintain stability and strong adhesion under extreme high and low temperature environments, and thus achieve a long-term stable bird-repelling effect, has become an urgent need to improve the protective durability of diversified outdoor public facilities and key industry production equipment. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a self-healing polymer fragrance-releasing material with dual ultraviolet light effects and its preparation method. Through the synergistic effect of the film-forming matrix and active ingredients, and with its dual-effect anti-ultraviolet design and high-quality filling system, this material significantly enhances its resistance to strong outdoor ultraviolet radiation, wind and rain, and severe temperature differences. At the same time, this material has a self-healing function, which can dynamically heal surface micro-cracks, prevent fragrance components from volatilizing too quickly, and ensure the continuous stability of its function.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a self-healing polymer fragrance-releasing material with dual ultraviolet light effects, wherein the polymer fragrance-releasing material is made by mixing film-forming base material A and active ingredient B.

[0007] The film-forming base material A comprises the following components in parts by weight: 45-55 parts acrylic resin, 4-6 parts hollow glass microspheres, 4-6 parts dextrin, 6-8 parts film-forming aid, 10-14 parts epoxy resin, and 8-12 parts deionized water.

[0008] The active ingredient B comprises the following components in parts by mass: 8-12 parts cinnamaldehyde, 8-12 parts methyl aminobenzoate, 2-3 parts allicin, 2-4 parts ultraviolet absorber, 2-4 parts ultraviolet blocker, and 18-22 parts deionized water.

[0009] Furthermore, the film-forming base material A also includes 1-2 parts of defoamer. This component is added to reduce air bubbles in the mixture, making the interior of the film-forming base material A as porous as possible, thus ensuring the slow-release effect during subsequent use.

[0010] Furthermore, the defoamer is a polyether-modified polysiloxane.

[0011] Furthermore, the film-forming aid is prepared by mixing 4-5 parts of rosin resin and 3-4 parts of sodium alginate in parts by weight.

[0012] Furthermore, the ultraviolet light absorber is 2-(2-hydroxy-5-benzyl)benzotriazole, and the ultraviolet light blocking agent is prepared by mixing nano-titanium dioxide and nano-zinc oxide in a mass ratio of 1:1.

[0013] The preparation method of the above-mentioned polymeric fragrance-releasing material includes the following steps: Step 1: Mix 45-55 parts acrylic resin, 4-6 parts hollow glass microspheres, and 8-12 parts deionized water in three batches according to the specified mass ratio. Each time, use a low stirring speed of 300-500 rpm and control the stirring temperature at 30℃-50℃ to form a mixture. Ensure that the acrylic resin is fully dissolved and the hollow glass microspheres are evenly distributed.

[0014] Step 2: Add 4-6 parts of dextrin and 6-8 parts of film-forming aid to the mixture according to the mass ratio, and continue the stirring process of Step 1 until it is evenly dispersed. Then add 10-14 parts of epoxy resin to further enhance the structure of the coating, and add 1-2 parts of defoamer to reduce the bubbles in the mixture. Stir at a speed of 500-800 r / min for 10 minutes to ensure that all components are fully mixed and uniform, and obtain film-forming base material A.

[0015] Step 3: Add 8-12 parts by weight of cinnamaldehyde, 8-12 parts by weight of methyl aminobenzoate and 2-3 parts by weight of allicin to 18-22 parts by weight of deionized water, and carry out emulsification reaction at a water temperature of 50℃-75℃; after emulsification, add 2-4 parts by weight of ultraviolet light absorber and 2-4 parts by weight of ultraviolet light blocker in sequence, and after full fusion, active ingredient B is formed.

[0016] Step 4: Mix the film-forming base material A formed in Step 2 with the active ingredient B formed in Step 3 at a mass ratio of 1:2 at room temperature, and stir at a speed of 1200 rpm for 5 to 6 minutes. After thorough mixing, a self-healing polymer fragrance-releasing material with dual ultraviolet light effects is formed.

[0017] Compared with the prior art, the present invention has the following advantages: 1. This invention adopts a dual-effect design combining ultraviolet light absorbers and ultraviolet light blockers to construct a dual-effect protection system of "absorption + shielding" which effectively delays the ultraviolet degradation and volatilization of fragrance-releasing components. Furthermore, the fragrance-releasing components are formed by the combination of cinnamaldehyde, methyl aminobenzoate, and allicin, ensuring that the fragrance-releasing material can maintain a stable fragrance-releasing effect even under long-term outdoor exposure, thus solving the bottleneck of short-term effectiveness of traditional bird-repelling materials.

[0018] 2. The polymeric fragrance-releasing material produced by this invention possesses self-healing capabilities, automatically repairing minute surface cracks and restoring the integrity and functionality of the fragrance-releasing material's surface layer upon damage. This function is primarily achieved through the dynamic hydrogen bond interactions generated in the composite network structure by polar groups such as hydroxyl and ether bonds in acrylic resin, epoxy resin, dextrin, and film-forming aids. This interaction allows the surface layer of the polymeric fragrance-releasing material to re-adsorb and heal at the molecular level, much like "glue," after mechanical damage. This characteristic enables the polymeric fragrance-releasing material to continuously provide fragrance release and maintain stability during long-term use, significantly improving its functional sustainability under conditions of wind, rain, and mechanical damage.

[0019] 3. The film-forming base material A prepared by this invention contains a large number of hydroxyl (-OH) groups and ether bonds. These polar groups form strong hydrogen bond adsorption with the substrate surface, while the wetting and permeability of acrylic resin can alleviate the volume shrinkage stress generated by epoxy resin during the curing process, thus constructing a composite network structure with excellent alternating stability and resistance to extreme cold embrittlement and high temperature softening. This enables the polymer fragrance release material to have good tolerance in high temperature, low temperature and high temperature alternating environments. Attached Figure Description

[0020] Figure 1 This is a flowchart illustrating the preparation process of the polymeric fragrance-releasing material in this invention.

[0021] Figure 2 This is a schematic diagram of the composite network structure of the polymer fragrance-releasing material prepared according to the present invention.

[0022] Figure 3 This is a schematic diagram illustrating the stability mechanism of the polymer fragrance-releasing material prepared according to the present invention under extreme environments. Detailed Implementation

[0023] The present invention will be further described below.

[0024] Example 1: As Figure 1 As shown, the preparation process in this embodiment includes the following steps: Step 1: Mix 45 parts acrylic resin, 4 parts hollow glass microspheres, and 8 parts deionized water in three batches according to the specified mass ratio. Each time, use a low stirring speed of 400 r / min and control the stirring temperature at 30℃ to form a mixture. Ensure that the acrylic resin is fully dissolved and the hollow glass microspheres are evenly distributed.

[0025] Step 2: Add 4 parts dextrin and 6 parts film-forming aid to the mixture according to the mass ratio, and continue the stirring process of Step 1 until it is evenly dispersed. Then add 10 parts epoxy resin to further enhance the structure of the coating, and add 1 part defoamer to reduce the bubbles in the mixture. Stir at 500 r / min for 10 minutes to ensure that all components are fully mixed and uniform, and obtain film-forming base material A.

[0026] Step 3: Add 8 parts by weight of cinnamaldehyde, 8 parts by weight of methyl aminobenzoate and 2 parts by weight of allicin to 18 parts by weight of deionized water, and carry out emulsification reaction at a water temperature of 50°C; after emulsification, add 2 parts by weight of ultraviolet light absorber and 2 parts by weight of ultraviolet light blocker in sequence, and after full fusion, active ingredient B is formed.

[0027] Step 4: Mix the film-forming base material A formed in Step 2 with the active ingredient B formed in Step 3 at a mass ratio of 1:2 at room temperature, and stir at 1200 rpm for 5 minutes. After thorough mixing, the ultraviolet light dual-effect self-healing polymer fragrance release material prepared in Example 1 is formed.

[0028] In this embodiment, the defoamer and deionized water together constitute auxiliary reagent C; the defoamer is polyether-modified polysiloxane; the film-forming aid is prepared by mixing 4 parts of rosin resin and 3 parts of sodium alginate according to the mass ratio; the ultraviolet light absorber is 2-(2-hydroxy-5-benzyl)benzotriazole; the ultraviolet light blocking agent is prepared by mixing nano titanium dioxide and nano zinc oxide in a mass ratio of 1:1.

[0029] Example 2: The preparation process of this example includes the following steps: Step 1: Mix 50 parts acrylic resin, 5 parts hollow glass microspheres, and 10 parts deionized water in three batches according to the specified mass ratio. Each time, use a low stirring speed of 400 r / min and control the stirring temperature at 40℃ to form a mixture. Ensure that the acrylic resin is fully dissolved and the hollow glass microspheres are evenly distributed.

[0030] Step 2: Add 5 parts dextrin and 7 parts film-forming aid to the mixture according to the mass ratio, and continue the stirring process of Step 1 until it is evenly dispersed. Then add 12 parts epoxy resin to further enhance the structure of the coating, and add 1.5 parts defoamer to reduce the bubbles in the mixture. Stir at 650 r / min for 10 minutes to ensure that all components are fully mixed and uniform, and obtain film-forming base material A.

[0031] Step 3: Add 10 parts by weight of cinnamaldehyde, 10 parts by weight of methyl aminobenzoate and 2.5 parts by weight of allicin to 20 parts by weight of deionized water, and carry out emulsification reaction at a water temperature of 65°C; after emulsification, add 3 parts by weight of ultraviolet light absorber and 3 parts by weight of ultraviolet light blocker in sequence, and after full fusion, active ingredient B is formed.

[0032] Step 4: Mix the film-forming base material A formed in Step 2 with the active ingredient B formed in Step 3 at a mass ratio of 1:2 at room temperature, and stir at 1200 rpm for 5 minutes. After thorough mixing, the ultraviolet light dual-effect self-healing polymer fragrance release material prepared in Example 2 is formed.

[0033] In this embodiment, the defoamer is a polyether-modified polysiloxane; the film-forming aid is prepared by mixing 4 parts of rosin resin and 4 parts of sodium alginate according to the mass ratio; the ultraviolet light absorber is 2-(2-hydroxy-5-benzyl)benzotriazole; and the ultraviolet light blocking agent is prepared by mixing nano titanium dioxide and nano zinc oxide in a mass ratio of 1:1.

[0034] Example 3: The preparation process of this example includes the following steps: Step 1: Mix 55 parts acrylic resin, 6 parts hollow glass microspheres, and 12 parts deionized water in three batches according to the specified mass ratio. Each time, use a low stirring speed of 500 r / min and control the stirring temperature at 50℃ to form a mixture. Ensure that the acrylic resin is fully dissolved and the hollow glass microspheres are evenly distributed.

[0035] Step 2: Add 6 parts dextrin and 8 parts film-forming aid to the mixture according to the mass ratio, and continue the stirring process of Step 1 until it is evenly dispersed. Then add 14 parts epoxy resin to further enhance the structure of the coating, and add 2 parts defoamer to reduce the bubbles in the mixture. Stir at 800 r / min for 10 minutes to ensure that all components are fully mixed and uniform, and obtain film-forming base material A.

[0036] Step 3: Add 12 parts by weight of cinnamaldehyde, 12 parts by weight of methyl aminobenzoate and 3 parts by weight of allicin to 22 parts by weight of deionized water, and carry out emulsification reaction at a water temperature of 75°C; after emulsification, add 4 parts by weight of ultraviolet light absorber and 4 parts by weight of ultraviolet light blocker in sequence, and after full fusion, active ingredient B is formed.

[0037] Step 4: Mix the film-forming base material A formed in Step 2 with the active ingredient B formed in Step 3 at a mass ratio of 1:2 at room temperature, and stir at a speed of 1200 rpm for 6 minutes. After thorough mixing, the ultraviolet light dual-effect self-healing polymer fragrance release material prepared in Example 2 is formed.

[0038] In this embodiment, the defoamer is a polyether-modified polysiloxane; the film-forming aid is prepared by mixing 5 parts of rosin resin and 3 parts of sodium alginate according to the mass ratio; the ultraviolet light absorber is 2-(2-hydroxy-5-benzyl)benzotriazole; and the ultraviolet light blocking agent is prepared by mixing nano-titanium dioxide and nano-zinc oxide in a mass ratio of 1:1.

[0039] Experiments have shown that: (1) High and low temperature and cycle tolerance test The coated panels, sprayed with the polymer fragrance-releasing materials of Examples 1 to 3, were placed in high and low temperature test chambers. Low temperature test: The coated panels were placed in a low-temperature chamber and cooled to -50°C for 168 hours. High temperature test: The coated panels were placed in an oven and heated to 50°C for 168 hours. High and low temperature cycling test: The temperature was lowered to -50°C and held for 24 hours, then raised to 50°C and held for 24 hours. After 5-10 cycles, the panels were removed, and the surface appearance of the material was observed, as shown in Table 1.

[0040] Table 1 As shown in the table above, the polymeric fragrance-releasing materials prepared in Examples 1 to 3 all exhibited excellent physical stability under extreme temperature conditions. Under continuous high or extremely cold environments, the coating maintained its appearance and a certain degree of elasticity, and after multiple cycles of intense high and low temperature alternation, no cracking, blistering, or peeling occurred. The reason for its good resistance is as follows: Figure 2 As shown, the strong adsorption between the polar groups in the film-forming base material A and the substrate, as well as the composite network structure constructed by acrylic acid and epoxy resin, can effectively resist extreme cold embrittlement and high temperature softening, ensuring the structural integrity of the coating under harsh outdoor climates.

[0041] (2) Self-healing test Micron-level wounds were made on the surface of the coating plates sprayed with the polymer fragrance-releasing materials of Examples 1 to 3 using a standard cross-cutting knife. The coating plates with wounds were placed in room temperature and high / low temperature chambers for 24 hours, respectively, and the scratches were observed under a 100x microscope. The healing efficiency was calculated as follows: Healing efficiency = (original wound length - remaining wound length after healing) / original wound length. The specific results are shown in Table 2.

[0042] Table 2 As shown in the table above, the healing efficiency of the polymeric fragrance-releasing materials prepared in Examples 1 to 3 remained at a high level under various environments, especially at room temperature where the healing efficiency approached 100%; even under extreme high or low temperature environments, the self-repair efficiency of the polymeric fragrance-releasing material coating remained stable at 95%. Figure 3As shown, the polymeric fragrance-releasing material prepared by this invention has excellent dynamic healing ability, which can automatically repair the microcracks caused by damage, thereby effectively locking in the active fragrance-releasing components inside and preventing a sudden reduction in fragrance release effect due to damage to the material surface, thus achieving long-lasting functionality.

[0043] (3) Bird deterrence test Two identical metal food containers were prepared. Container A (control group): no material was used; Container B (experimental group): its outer wall and perimeter were coated sequentially with the polymeric aroma-releasing materials prepared in Examples 1 to 3. 60g of equal amounts of grains, mealworms, and other bird-preferred foods were placed in both Container A and Container B coated with Example 1. The 30 experimental birds were then fasted for 4 hours. Monitoring cameras recorded the total amount of food consumed in each container over 48 hours (calculated by weight difference), the number of landing attempts, and the number of successful feedings. The avoidance rate was calculated as [1 - (food consumed in Container B / food consumed in Container A)] × 100%. The above experimental procedure was repeated for Container B coated with Example 2 and Container B coated with Example 3, respectively. The specific results are shown in Table 3.

[0044] Table 3 As shown in the table above, the experimental group (box B) coated with the polymeric fragrance-releasing material prepared in any embodiment of the present invention had a much lower food intake than the control group within 48 hours. Among them, the repellency rate of Example 1 was the highest, reaching 96%, while the repellency rate of Example 2 was the lowest among the three examples, but it still exceeded 90%. This demonstrates that the polymeric fragrance-releasing material prepared in the present invention has an excellent bird-repelling effect.

[0045] (4) Artificial accelerated aging test Referring to GB / T14522-1993 "Artificial Climate Accelerated Test Method for Plastics, Coatings and Rubber Materials for Mechanical Industry Products", an ultraviolet fluorescent lamp climate aging test chamber equipped with an automatic spraying system was used to test the coating surface of the paint plate sprayed with the polymer fragrance-releasing material prepared in Examples 1 to 3. UVB-313 lamp tubes were used, and continuous irradiation was carried out for 14 days, with water spraying every 4 hours. The mass loss rate was calculated as (initial mass of material - remaining mass of material) / initial mass of material.

[0046] Table 4 As shown in the table above, during the accelerated aging process simulated by long-term UV exposure and rain erosion, the coating's mass loss rate was extremely low, only about 4% to 5% after 14 days, and the coating surface remained intact without any chalking. This indicates that the "absorption + shielding" dual-effect protection system, composed of UV absorbers and UV blockers, played a crucial role. This system effectively delayed the UV degradation and volatilization of active ingredients in the fragrance-releasing material, significantly improving the material's outdoor weather resistance.

[0047] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A self-healing polymer fragrance-releasing material with dual ultraviolet light effects, characterized in that, The polymeric fragrance-releasing material is made by mixing film-forming base material A and active ingredient B; The film-forming base material A comprises the following components in parts by weight: 45-55 parts acrylic resin, 4-6 parts hollow glass microspheres, 4-6 parts dextrin, 6-8 parts film-forming aid, 10-14 parts epoxy resin, and 8-12 parts deionized water. The active ingredient B comprises the following components in parts by mass: 8-12 parts cinnamaldehyde, 8-12 parts methyl aminobenzoate, 2-3 parts allicin, 2-4 parts ultraviolet absorber, 2-4 parts ultraviolet blocker, and 18-22 parts deionized water.

2. The polymeric fragrance-releasing material according to claim 1, characterized in that, The film-forming base material A also includes 1-2 parts of defoamer.

3. The polymeric fragrance-releasing material according to claim 2, characterized in that, The defoamer is a polyether-modified polysiloxane.

4. The polymeric fragrance-releasing material according to claim 1, characterized in that, The film-forming aid is prepared by mixing 4-5 parts of rosin resin and 3-4 parts of sodium alginate in parts by weight.

5. The polymeric fragrance-releasing material according to claim 1, characterized in that, The ultraviolet light absorber is 2-(2-hydroxy-5-benzyl)benzotriazole, and the ultraviolet light blocking agent is prepared by mixing nano-titanium dioxide and nano-zinc oxide in a mass ratio of 1:

1.

6. A method for preparing a polymeric fragrance-releasing material according to any one of claims 1 to 5, characterized in that, Includes the following steps: Step 1: Mix 45-55 parts acrylic resin, 4-6 parts hollow glass microspheres and 8-12 parts deionized water in three batches according to the mass ratio. Each time, use a low stirring speed of 300-500 r / min and control the stirring temperature at 30℃-50℃ to form a mixture. Step 2: Add 4-6 parts of dextrin and 6-8 parts of film-forming aid to the mixture according to the mass ratio, and continue the stirring process of Step 1 until it is evenly dispersed. Then add 10-14 parts of epoxy resin and 1-2 parts of defoamer. Stir at a speed of 500-800 r / min for 10 minutes to ensure that all components are fully mixed and uniform, and obtain film-forming base material A. Step 3: Add 8-12 parts by weight of cinnamaldehyde, 8-12 parts by weight of methyl aminobenzoate and 2-3 parts by weight of allicin to 18-22 parts by weight of deionized water, and carry out emulsification reaction at a water temperature of 50℃-75℃; after emulsification, add 2-4 parts by weight of ultraviolet light absorber and 2-4 parts by weight of ultraviolet light blocker in sequence, and after full fusion, active ingredient B is formed. Step 4: Mix the film-forming base material A formed in Step 2 with the active ingredient B formed in Step 3 at a mass ratio of 1:2 at room temperature, and stir at a speed of 1200 rpm for 5 to 6 minutes. After thorough mixing, a self-healing polymer fragrance-releasing material with dual ultraviolet light effects is formed.

7. An application of the polymeric fragrance-releasing material prepared according to claim 1 as a bird-repelling material.

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