A double anti-counterfeiting polyester amide composite material and a preparation method and application thereof
By combining modified long afterglow powder with polyesteramide, a dual anti-counterfeiting polyesteramide composite material was prepared, which solved the problem of limited color and stimulus form in anti-counterfeiting materials, achieved multiple anti-counterfeiting features and editable colors, and improved the safety and degradation performance of the material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ANHUI AGRICULTURAL UNIVERSITY
- Filing Date
- 2023-11-03
- Publication Date
- 2026-06-30
Smart Images
Figure CN117363008B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of anti-counterfeiting materials technology, specifically to a dual anti-counterfeiting polyesteramide composite material, its preparation method, and its application. Background Technology
[0002] Information security is a crucial consideration in our daily lives, significantly impacting society, the economy, and technology. Each major innovation in anti-counterfeiting technology represents a new step forward in ensuring the security of confidential information. Stimulated luminescent materials, due to their simple manufacturing process and high visibility, are receiving increasing attention and are considered the optimal technological choice for modern anti-counterfeiting and encryption.
[0003] In recent years, various luminescent materials based on light, heat, and electricity stimulation have been widely used in product anti-counterfeiting and information encryption. However, regrettably, a single luminescent color and a single stimulus response are easily duplicated by existing anti-counterfeiting materials, leading to reduced anti-counterfeiting performance and making products easier for counterfeiters to forge. Clearly, if the luminescent color and stimulus form of a material could be diversified in response to different external stimuli, the security of encrypted information would be greatly improved. Therefore, the creation of multi-layered anti-counterfeiting materials is considered a key method to solve this problem.
[0004] Chinese patent application CN115286788A discloses a polyolefin-based bio-based polyesteramide and its preparation method. The preparation method includes the following steps: dissolving a bio-based diester and an amino alcohol in a solvent, adding a catalyst under inert gas protection to obtain an amide diol monomer; placing the amide diol monomer and a bio-based diacid in a reaction apparatus and carrying out an esterification reaction under an inert gas atmosphere to obtain a prepolymer; adding a diol and a catalyst, carrying out an esterification reaction under an inert gas atmosphere; depressurizing to remove water, and then heating to obtain the polyolefin-based bio-based polyesteramide. The thermodynamic properties of the polyesteramide can be controlled by adjusting different amide diols and the molar ratio of alcohol to acid in the polymer. The prepared polyesteramide exhibits excellent performance, reaching the level of high-density polyethylene, and is expected to serve as a substitute for petroleum-based polyethylene. However, its degradation performance is poor, and its use as an anti-counterfeiting material is not disclosed. Summary of the Invention
[0005] The technical problem to be solved by this invention is how to improve the anti-counterfeiting performance and degradation performance of anti-counterfeiting materials.
[0006] The present invention solves the above-mentioned technical problems through the following technical means:
[0007] A method for preparing a dual anti-counterfeiting polyester amide composite material includes the following steps:
[0008] S1. The long afterglow powder was modified by using an aminosilane coupling agent as a modifier to obtain the modified long afterglow powder.
[0009] S2. Using amide diol and azelaic acid as raw materials, a primary reaction is carried out under inert gas and stirring conditions, followed by heating. After the reaction, the mixture is cooled to room temperature, polyetheramine and a catalyst are added, and then a secondary reaction is carried out under inert gas and stirring conditions. After the reaction, the mixture is cooled to obtain polyesteramide. The structural formula of the amide diol is:
[0010] S3. The modified long afterglow powder in S1 and the polyesteramide in S2 are ball-milled and mixed in a cryogenic ball mill, and then the ball-milled product is hot-pressed to obtain the dual anti-counterfeiting polyesteramide composite material.
[0011] Preferably, in S1, the aminosilane coupling agent is 3-aminopropyltriethoxysilane; and the long afterglow powder is one or more of PLO long afterglow powder, PLP long afterglow powder, and REO-1 long afterglow powder.
[0012] Preferably, in S1, the ratio of the long afterglow powder to the aminosilane coupling agent is 1g:2ml.
[0013] Preferably, in S2, the polyetheramine is polyetheramine D-400; and the catalyst is sodium hypophosphite.
[0014] Preferably, in S2, the mass ratio of the amide diol, azelaic acid, and polyetheramine is 38.11:27.92:11.75; the mass ratio of the azelaic acid and the catalyst is 27.92:0.5; the temperature of the first reaction is 140°C and the time is 12 hours; the temperature of the second reaction is 230°C and the time is 3 hours.
[0015] Preferably, in S3, the mass ratio of the modified long afterglow powder to polyesteramide is 0.1-0.4:10.
[0016] Preferably, in step S3, the hot-pressed products prepared from various modified long afterglow powders are combined and stacked, and then heated to obtain the dual anti-counterfeiting polyesteramide composite material.
[0017] Beneficial effects: By combining and stacking various hot-pressed products prepared with different modified long afterglow powders, and then heating and laminating them, the resulting film product has editable color, providing a wider range of anti-counterfeiting color options for the film, which is a double anti-counterfeiting polyesteramide material.
[0018] Preferably, in S1, two or three long afterglow powders are modified with an aminosilane coupling agent to obtain two or three modified long afterglow powders; in S3, the two or three modified long afterglow powders obtained in S1 are ball-milled and mixed with the polyesteramide in S2 in a cryogenic ball mill, and then the ball-milled products are hot-pressed to obtain two or three different hot-pressed films. The two or three different hot-pressed films are combined and stacked, and then the combined and stacked sample is heated at 60°C for 2 hours under the condition of being pressed by a glass plate, and then cooled to obtain the double anti-counterfeiting polyesteramide composite material.
[0019] Preferably, S1 specifically includes the following steps: mixing long afterglow powder, ethanol, and water, stirring, then sonicating, adding an aminosilane coupling agent, sonicating and stirring again, then filtering, washing, and drying to obtain the modified long afterglow powder.
[0020] The present invention also proposes a dual anti-counterfeiting polyester amide composite material, which is prepared by the aforementioned method for preparing dual anti-counterfeiting polyester amide composite material.
[0021] The present invention also proposes the application of the aforementioned dual anti-counterfeiting polyester amide composite material in anti-counterfeiting packaging.
[0022] The advantages of this invention are:
[0023] (1) The material of the present invention achieves editable material color through color overlap, which solves the problem of single color and single anti-counterfeiting method of current luminescent material. At the same time, the stretch-induced crystallization of polymer gives it the ability to shrink thermally. Through polymer structural characteristics and color editing, the polymer achieves double anti-counterfeiting coding. Combining this property, it has potential application prospects in double anti-counterfeiting packaging film.
[0024] (2) The performance of the material of the present invention can be controlled by adjusting the composite ratio of long afterglow pigment and polymer;
[0025] (3) In this invention, long-afterglow pigments are modified and combined with bio-based polymers to achieve the reinforcement of polymers by long-afterglow inorganic polymers. At the same time, alternating polyesteramide blocks are introduced into the main chain of polyesteramide polymers to give the material excellent degradability. The polyesteramide anti-counterfeiting material prepared in this way has excellent degradability. Attached Figure Description
[0026] Figure 1 Infrared spectra of PLO and modified long afterglow powder used in Example 1 of this invention;
[0027] Figure 2 A physical image of Example 7 prepared using the products of Examples 1 and 4 of this invention;
[0028] Figure 3 The stress-strain curves of the products of Examples 4-8 of this invention are shown.
[0029] Figure 4 This is a bar chart showing the maximum fracture stress of the products from Examples 4-8 of the present invention;
[0030] Figure 5 Color-edited images of products from Examples 7(A), 9(B), and 10(C) of this invention stacked together;
[0031] Figure 6 This is an image of the product of Example 7 of the present invention, showing stretch-induced crystallization.
[0032] Figure 7 This is a demonstration of the thermal shrinkage performance of the product in Example 7 of the present invention;
[0033] Figure 8 Images showing the color editing and heat shrinkage of the product of Example 9 of the present invention after stretching and using it as a substrate;
[0034] Figure 9 The infrared spectrum of the product of Example 4 of this invention;
[0035] Figure 10 These are scanning electron microscope images of the materials before and after enzymatic hydrolysis in Example 4 and Comparative Example 1 of the present invention;
[0036] Figure 11 These are actual images of the product from Example 4 of the present invention after enzymatic hydrolysis for 4, 6, and 8 days. Detailed Implementation
[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0038] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.
[0039] Unless otherwise specified in the embodiments, the techniques or conditions described in the literature in this field or in accordance with the product manual may be followed.
[0040] The amide diol mentioned in the following examples is the amide diol disclosed in Chinese patent application document CN115286788A, and its structural formula is as follows: It was prepared according to the method described in the literature.
[0041] The PLO long afterglow powder, PLP long afterglow powder, and REO-1 long afterglow powder were purchased from Lumin Technology Group Co., Ltd.
[0042] Example 1
[0043] A method for modifying long afterglow powder includes the following steps: Take 20g of PLO long afterglow powder, 80ml of ethanol, and 80ml of water and add them to a 250ml glass beaker. Stir for 30min, then sonicate for 30min. Then add 40ml of 3-aminopropyltriethoxysilane, sonicate for 30min, stir for 4h, filter, wash with water 3 times, and dry to obtain the modified long afterglow powder.
[0044] Example 2
[0045] A method for modifying long afterglow powder includes the following steps: 20g of PLP long afterglow powder, 80ml of ethanol, and 80ml of water are added to a 250ml glass beaker, stirred for 30min, then sonicated for 30min, followed by the addition of 40ml of 3-aminopropyltriethoxysilane, sonicated for 30min, stirred for 4h, then filtered, washed three times with water, and dried to obtain the modified long afterglow powder.
[0046] Example 3
[0047] A method for modifying long afterglow powder includes the following steps: Take 20g of REO-1 long afterglow powder, 80ml of ethanol, and 80ml of water and add them to a 250ml glass beaker. Stir for 30min, then sonicate for 30min. Then add 40ml of 3-aminopropyltriethoxysilane, sonicate for 30min, stir for 4h, filter, wash with water 3 times, and dry to obtain the modified long afterglow powder.
[0048] Example 4
[0049] A method for preparing polyesteramide includes the following steps: 38.11g of amide diol and 27.92g of azelaic acid are added to a 250ml three-necked round-bottom flask. Under flowing nitrogen and mechanical stirring, the temperature is gradually increased to 140℃ and reacted for 12 hours. Then, the product in the round-bottom flask is cooled to room temperature. Subsequently, 11.75g of polyetheramine D-400 and 500mg of sodium hypophosphite are added. Then, under flowing nitrogen and mechanical stirring, the temperature is gradually increased to 230℃ and reacted for 3 hours. The temperature is then reduced to 160℃, and the polyesteramide is obtained.
[0050] Example 5
[0051] A method for preparing a dual anti-counterfeiting polyesteramide composite material includes the following steps: 0.1g of the long afterglow powder modified in Example 1 and 10g of the polyesteramide prepared in Example 4 are mixed and ball-milled in a cryogenic ball mill. The ball-milled product is then heated at 200°C for 3 minutes and then pressurized for 3 minutes for hot pressing. After cooling to 60°C, the product is removed to obtain the dual anti-counterfeiting polyesteramide composite material.
[0052] Example 6
[0053] A method for preparing a dual anti-counterfeiting polyesteramide composite material includes the following steps: 0.2g of the long afterglow powder modified in Example 1 and 10g of the polyesteramide prepared in Example 4 are mixed and ball-milled in a cryogenic ball mill. The ball-milled product is then heated at 200°C for 3 minutes and then pressurized for 3 minutes for hot pressing. After cooling to 60°C, the product is removed to obtain the dual anti-counterfeiting polyesteramide composite material.
[0054] Example 7
[0055] A method for preparing a dual anti-counterfeiting polyesteramide composite material includes the following steps: 0.3g of the long afterglow powder modified in Example 1 and 10g of the polyesteramide prepared in Example 4 are mixed and ball-milled in a cryogenic ball mill. The ball-milled product is then heated at 200°C for 3 minutes and then pressurized for 3 minutes for hot pressing. After cooling to 60°C, the product is removed to obtain the dual anti-counterfeiting polyesteramide composite material.
[0056] Example 8
[0057] A method for preparing a dual anti-counterfeiting polyesteramide composite material includes the following steps: 0.4g of the long afterglow powder modified in Example 1 and 10g of the polyesteramide prepared in Example 4 are mixed and ball-milled in a cryogenic ball mill. The ball-milled product is then heated at 200°C for 3 minutes and then pressurized for 3 minutes for hot pressing. After cooling to 60°C, the product is removed to obtain the dual anti-counterfeiting polyesteramide composite material.
[0058] Example 9
[0059] A method for preparing a dual anti-counterfeiting polyesteramide composite material includes the following steps: 0.3g of the long afterglow powder modified in Example 2 and 10g of the polyesteramide prepared in Example 4 are mixed and ball-milled in a cryogenic ball mill. The ball-milled product is then heated at 200°C for 3 minutes and then pressurized for 3 minutes for hot pressing. After cooling to 60°C, the product is removed to obtain the dual anti-counterfeiting polyesteramide composite material.
[0060] Example 10
[0061] A method for preparing a dual anti-counterfeiting polyesteramide composite material includes the following steps: 0.3g of the long afterglow powder modified in Example 3 and 10g of the polyesteramide prepared in Example 4 are mixed and ball-milled in a cryogenic ball mill. The ball-milled product is then heated at 200°C for 3 minutes and then pressurized for 3 minutes for hot pressing. Afterward, it is cooled to 60°C and removed to obtain the dual anti-counterfeiting polyesteramide composite material.
[0062] Comparative Example 1
[0063] Polybutylene terephthalate (Mn = 120000) was purchased from Maclean Reagents Co., Ltd.
[0064] In Example 4 of this invention, the polymerization scheme for polyesteramide employs a two-stage method. The first stage involves prepolymerization of the amide diol and diacid at 140°C. This is primarily because the diol undergoes self-polymerization into ether at high temperatures, leading to uneven feed ratios and reduced material performance. Therefore, the first stage of polymerization in this invention utilizes a low-temperature, long-duration polymerization method. The second stage involves adding polyetheramine after the first stage has cooled to room temperature. This is mainly because adding at high temperatures would cause product oxidation. Furthermore, after cooling to room temperature, the prepolymer from the first stage solidifies, allowing for accurate weighing of the added liquid polyetheramine in the second stage. Any excess can be directly extracted, preventing imbalances in the feed ratio.
[0065] The preparation of this anti-counterfeiting material consists of two parts. The first part involves blending modified long-afterglow powder with polyesteramide in a cryogenic ball mill. Compared to screw extrusion blending, ball mill blending offers advantages in terms of speed and simplicity. The reason for using cryogenic ball milling is that heat is generated during the ball milling process, causing the plastic to soften and become unbreakable. The second part involves hot pressing the blended powder into a film using a hot press. The modified long-afterglow powder is filled with primary amine groups, which can form hydrogen bonds with ester and amide bonds in the polymer, thereby enhancing the polymer's properties.
[0066] A physical image of the product from Example 4 is shown below. Figure 2 As shown, it is a crystallization-induced whitening state. Figure 9 The presence of peaks for amide and ester bonds in the infrared spectrum, together with the above, proves the successful preparation of polyesteramide in Example 4.
[0067] The alternating arrangement of ester and amide bonds in the structure of polyesteramide elastomers endows the polymer with excellent degradability. Simultaneously, the introduction of side groups in the soft segments disrupts the original crystallinity of the polymer, resulting in a faster degradation rate. To better demonstrate the degradation rate of Example 4, Comparative Example 1 was selected as a control. The materials from Example 4 and Comparative Example 1 were placed in sterile PBS buffer (pH = 7.2) containing 1 wt% Novozymes 435 enzyme and heated in a water bath at 37°C using a shaker. The results are as follows... Figure 10 As shown, from Figure 10 It can be seen that the material in Example 4 exhibited a large number of porous structures after only two days of soaking, indicating severe degradation with a degradation rate reaching 80%. After an extended soaking time of eight days, it completely formed debris. Figure 11 As shown in the figure. However, the material in Comparative Example 1 showed gradual degradation with increasing soaking time. Even after 12 days of soaking, it retained its original morphology, with only a large number of gaps appearing. This indicates that the polyesteramide elastomer synthesized by this method has the ability to degrade rapidly.
[0068] pass Figure 1 The infrared spectrum shows that PLO, after the reaction, at 3500 cm⁻¹ -1 The characteristic peaks appearing at the point belong to primary amine groups, indicating that the primary amine groups were successfully attached to the long afterglow powder, demonstrating the successful preparation of Example 1.
[0069] In Example 7, the products of Example 1 and Example 4 were blended and then cryo-ball-milled. The mixture was then hot-pressed by heating at 200°C for 3 minutes followed by pressurization for 3 minutes, and subsequently cooled to 60°C to obtain a double anti-counterfeiting polymer film. Figure 2 As shown.
[0070] like Figure 3 As shown, the uniaxial tensile properties of the products of Examples 4-8 were tested at a tensile speed of 50 mm / min at room temperature. Introducing the product of Example 1 into the product of Example 4 allows for the regulation of the mechanical properties of the polyesteramide polymer. The general trend is that the mechanical properties first increase and then decrease with increasing content of the product of Example 1. For a more intuitive description, as shown... Figure 4 As shown, the maximum uniaxial fracture stress first increases and then decreases. This is because the low content of long-afterglow powder in the polymer is enhanced by the hydrogen bonding of the primary amine. When the content is too high, there are too many long-afterglow particles, which cannot interact with the polymer, thus leading to a decrease in mechanical properties.
[0071] The products from Examples 7, 9, and 10 were designated A, B, and C, respectively. They were freely combined and covered with a glass plate, then heated in a 60°C oven for 2 hours, where they bonded together through molecular chain movement to form a single unit. The unit was then placed in a dark room and irradiated with 365nm ultraviolet light, and photographs were taken before and after the lights were turned off. Figure 5 As shown, combining the products of Examples 7, 9, and 10 of the three colors yields 29 different colors. Meanwhile, Example 4 did not contain long-afterglow pigments, so it cannot be seen after the UV lamp is turned off. Among the different combinations in the figure, the material represented by the leftmost letter is closer to the UV lamp when irradiated with UV light.
[0072] The product of Example 7 was stretched, and a two-dimensional wide-angle test revealed crystallization after stretching. Figure 6 As shown, the top image represents the sample before stretching, and the bottom image represents the sample after stretching. Based on this, a heat shrinkage experiment was conducted. The stretched sample shrank after being heated at 60℃ for 10 seconds, indicating that the stretch-induced crystallization can be broken down by heating, thus imparting heat shrinkage properties to the material. Figure 7 ),in Figure 7 The middle right figure shows that even when pulled by a heavy object, it can still thermally shrink when heated.
[0073] Since the anti-counterfeiting material also has color editing and heat shrinking capabilities, we designed a dual anti-counterfeiting strip, such as... Figure 8 As shown, after stretching the material prepared in Example 9, stretched versions of Example 7 and / or Example 10 are attached to different positions on it to obtain a color-editable strip. After heating the strip, the strip shrinks. This design is expected to be applied to anti-counterfeiting packaging. In the figure, the upper strip was photographed under 365nm ultraviolet light, and the lower strip was photographed after the ultraviolet light was turned off.
[0074] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for preparing a dual anti-counterfeiting polyesteramide composite material, characterized in that: Includes the following steps: S1. The long afterglow powder was modified by using an aminosilane coupling agent as a modifier to obtain the modified long afterglow powder. S2. Using amide diol and azelaic acid as raw materials, a primary reaction is carried out under inert gas and stirring conditions, followed by heating. After the reaction, the mixture is cooled to room temperature, polyetheramine and a catalyst are added, and then a secondary reaction is carried out under inert gas and stirring conditions. After the reaction, the mixture is cooled to obtain polyesteramide. The structural formula of the amide diol is: The mass ratio of the amide diol, azelaic acid, and polyetheramine is 38.11:27.92:11.75; the temperature of the first reaction is 140°C and the time is 12 hours; the temperature of the second reaction is 230°C and the time is 3 hours. S3. The modified long afterglow powder in S1 and the polyesteramide in S2 are ball-milled and mixed in a cryogenic ball mill. The ball-milled product is then hot-pressed. Multiple hot-pressed products prepared with different modified long afterglow powders are combined and stacked, and then heated to obtain the dual anti-counterfeiting polyesteramide composite material.
2. The preparation method of the dual anti-counterfeiting polyesteramide composite material according to claim 1, characterized in that: In S1, the aminosilane coupling agent is 3-aminopropyltriethoxysilane; the long afterglow powder is one or more of PLO long afterglow powder, PLP long afterglow powder, and REO-1 long afterglow powder.
3. The preparation method of the dual anti-counterfeiting polyesteramide composite material according to claim 1, characterized in that: In S1, the ratio of the long afterglow powder to the aminosilane coupling agent is 1g:2ml.
4. The preparation method of the dual anti-counterfeiting polyesteramide composite material according to claim 1, characterized in that: In S2, the polyetheramine is polyetheramine D-400; the catalyst is sodium hypophosphite.
5. The preparation method of the dual anti-counterfeiting polyesteramide composite material according to claim 1, characterized in that: In S2, the mass ratio of azelaic acid to catalyst is 27.92:0.
5.
6. The method for preparing the dual anti-counterfeiting polyesteramide composite material according to claim 1, characterized in that: In S3, the mass ratio of the modified long afterglow powder to polyesteramide is 0.1-0.4:
10.
7. The method for preparing the dual anti-counterfeiting polyesteramide composite material according to any one of claims 1-6, characterized in that: In S1, two or three long afterglow powders are modified with an aminosilane coupling agent to obtain two or three modified long afterglow powders. In S3, the two or three modified long afterglow powders obtained in S1 are ball-milled and mixed with the polyesteramide in S2 in a cryogenic ball mill. The ball-milled products are then hot-pressed to obtain two or three different hot-pressed films. The two or three different hot-pressed films are combined and stacked. The combined and stacked samples are then heated at 60°C for 2 hours under the condition of being pressed by a glass plate, and then cooled to obtain the dual anti-counterfeiting polyesteramide composite material.
8. A dual anti-counterfeiting polyesteramide composite material, characterized in that: It is prepared by the method for preparing dual anti-counterfeiting polyesteramide composite material as described in any one of claims 1-7.
9. The application of the double anti-counterfeiting polyesteramide composite material as described in claim 8 in anti-counterfeiting packaging.