Fluorescent antibacterial polymer taking natural extract curcumin as raw material and application of fluorescent antibacterial polymer in fluorescent fiber
By using fluorescent antibacterial polymers synthesized by the natural extract curcumin, combined with melt granulation and spinning technology, the problem of poor compatibility in the preparation of fluorescent fibers is solved, and the good luminous and mechanical properties of fluorescent fibers are improved.
Patent Information
- Application Number
- CN202411638178.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-16
- Publication Date
- 2025-02-25
AI Technical Summary
In the preparation of existing fluorescent fibers, the fluorescent dye has poor compatibility with the polymer matrix of the fiber, resulting in uneven dispersion, difficulty in spinning, degraded mechanical properties and poor environmental resistance of optical properties.
Develop a fluorescent antibacterial polymer synthesized from the natural extract curcumin and prepare fluorescent fibers through melt granulation and melt spinning techniques to ensure good compatibility of curcumin polymer with resin matrix.
It has achieved good luminescence performance, uniform structure stability and improved mechanical properties of fluorescent fibers, solved the problem of poor spinning properties of fluorescent fibers, and has broad application prospects.
Smart Images
Figure CN119505222A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of functional fibers, and specifically, develops a fluorescent polymer with good compatibility as a dye to prepare fluorescent fibers. Background Art
[0002] Fluorescent fiber is a kind of anti-counterfeiting fiber that has been studied a lot. It can be combined with trademarks, labels or packaging materials by weaving, bonding, embroidery, etc. It can be combined with books and certificates by binding thread, or it can be added to pulp in the form of short fibers to prepare anti-counterfeiting paper. Therefore, fluorescent fiber has a wide range of applications in luminous textiles, military, bioengineering and medical products. Fluorescent fiber is limited by the preparation method and is not common in the fiber market. Among the fiber preparation methods, the melt spinning method is simple and the process technology is mature, which can achieve large-scale continuous production, but it is still difficult to apply it to the production of fluorescent fibers. Commonly used fluorescent dyes are mainly rare earth inorganic phosphors, which have poor compatibility with the polymer matrix of the fiber and uneven distribution, making spinning difficult, easy to fly and break, and the mechanical properties of the fiber are reduced, and the optical properties have poor environmental resistance. Therefore, the development of fluorescent polymers with good compatibility with the resin matrix as dyes can solve the problems of uneven dispersion of fluorescent dyes and poor spinnability of fluorescent fibers from the source, thereby realizing the large-scale preparation of fluorescent fibers. Under the background of the “dual carbon” goals, preparing fluorescent polymer dyes using renewable natural extracts as raw materials is of great significance to alleviating resource shortages and environmental pollution. Summary of the invention
[0003] The purpose of the present invention is to provide a fluorescent antibacterial polymer made of natural extract curcumin as a raw material and its application in fluorescent fiber. The fluorescent polymer is melt-granulated to obtain a fluorescent masterbatch, which is added to fiber slices for melt spinning to prepare fluorescent fibers. The fiber has good luminous properties, uniform and stable structure, and good mechanical properties.
[0004] The purpose of the present invention is achieved through the following solutions:
[0005] In one aspect, the present invention is a curcumin polymer synthesized from a natural extract, curcumin, characterized in that the curcumin polymer has a structural formula of:
[0006]
[0007] Furthermore, the curcumin polymer has aggregation-induced emission effect and antibacterial effect.
[0008] Furthermore, the curcumin polymer is characterized in that the curcumin polymer has good antibacterial properties.
[0009] On the other hand, the present invention also provides a method for preparing the curcumin polymer.
[0010]
[0011] The preparation method of the curcumin polymer specifically comprises the following steps:
[0012] In a Schlenk tube filled with CsCO3, curcumin and 1,3-di(bromomethyl)benzene are added and dissolved in THF to obtain a mixed solution, and the mixed solution is placed in air at 70°C and slowly stirred for reaction for 24 hours. After 24 hours, the reaction solution is cooled to room temperature; CsCO3 in the reaction solution is filtered to obtain a mixed solution, and the mixed solution is concentrated under reduced pressure to obtain a product precipitate; the product is precipitated in excess petroleum ether, filtered and vacuum dried to obtain a yellow solid powder, i.e., curcumin polymer.
[0013] The application of the curcumin polymer or the preparation method of the curcumin polymer in the preparation of fluorescent fibers of the present invention comprises the following steps:
[0014] Step 1: The curcumin polymer or the curcumin polymer prepared by the above preparation method is mixed evenly with a resin matrix in a certain ratio, put into a twin-screw extruder, melt-extrude under the conditions of a certain temperature, feed speed, and main screw speed, and granulate through a granulator to obtain a fluorescent masterbatch;
[0015] Step 2: The fluorescent masterbatch and spinning chips obtained in step 1 are used as raw materials, and after drying, they are put into a melt spinning machine in a certain proportion, and are drawn into filaments at a certain temperature, screw speed, and drawing speed to obtain fluorescent fibers.
[0016] In the above step 1 of the present invention, the mixing ratio of curcumin polymer to resin matrix is 0.2-10 phr, the type of resin matrix is selected from one of PA6, PP and PET, the temperature of the twin-screw extruder is 80-280° C., the main screw speed is 150-250 rpm, the feeding screw speed is 10-40 rpm, and the granulator speed is 50-200 rpm. In step 2, the temperature of the melt spinning machine is 120-280° C.
[0017] The fluorescent fiber prepared by the above preparation method of the present invention is characterized in that the fiber fineness of the fluorescent fiber is in the range of 0.20 to 0.40 mm, emits yellow fluorescence under a 365nm ultraviolet lamp, and the fluorescent fiber is evenly distributed.
[0018] The beneficial effects of the present invention are: providing a fluorescent antibacterial polymer made of natural extract curcumin as a raw material and its application in fluorescent fiber. The fluorescent fiber prepared by the present invention has good luminescence characteristics, good mechanical properties, and uniform and stable structure. It can be widely used in the fields of luminous textiles, military, bioengineering and medical products, and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the curcumin polymer synthesized in specific embodiment 1 of the present invention;
[0020] Figure 2 This is the aggregation-induced emission effect of the curcumin polymer synthesized in specific embodiment 1 of the present invention in THF / water mixed solutions with different volume ratios.
[0021] Figure 3 This is a digital photo of the antibacterial effect experiment of the curcumin polymer synthesized in specific embodiment 1 of the present invention.
[0022] Figure 4 This is a digital photograph of the surface structure of the fluorescent fiber prepared in specific embodiment 2 of the present invention under sunlight and UV light observed through a microscope. DETAILED DESCRIPTION
[0023] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
[0024] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.
[0025] Example 1
[0026] Preparation of polymer dyes:
[0027] In a Schlenk tube filled with CsCO3 (3.3mmmol, 3equiv), curcumin (1.1mmol, 1equiv) and 1,3-di(bromomethyl)benzene (2.2mmol, 2equiv) were added and dissolved in THF (5mL). The mixed solution was placed in air at 70°C and slowly stirred for 24h. After 24h, the reaction solution was cooled to room temperature. Then, the CsCO3 in the reaction solution was filtered to obtain a mixed solution, and the mixed solution was concentrated to 2mL under reduced pressure. The product was precipitated in excess petroleum ether, filtered and vacuum dried to obtain a yellow solid powder of curcumin polymer.
[0028] The fluorescence spectra of the prepared curcumin polymer in mixed solutions with different water contents were measured. The product showed aggregation-induced emission effect in mixed solutions of THF / water with different volume ratios, see Appendix Figure 2 .Depend on Figure 2It can be seen that in the mixed solutions of different THF / water volume ratios, as the content of the poor solvent (water) increases, the curcumin polymer gradually precipitates to form nano-aggregates. As the degree of aggregation increases, the intensity of the fluorescence emission curve gradually increases, showing an obvious aggregation-induced emission effect.
[0029] Example 2
[0030] Preparation of fluorescent nylon 6 fiber:
[0031] Step (1): The curcumin polymer and PA6 prepared in Example 1 are used as raw materials. PA6 is placed in a rotary drum drying oven for drying. The dried PA6 and curcumin polymer are mixed uniformly in a certain ratio, put into a twin-screw extruder, melt-extruded under certain temperature, feed speed, and main screw speed, and granulated by a granulator to obtain fluorescent masterbatch.
[0032] Step (2): The fluorescent masterbatch and spinning chips obtained in step (1) are used as raw materials, and after drying, they are put into a melt spinning machine in a certain proportion, and are drawn into filaments at a certain temperature, screw speed, and drawing speed to obtain fluorescent fibers.
[0033] The drying time in step (1) is 10 hours, and the moisture content after drying is ≤100ppm; the amount of curcumin polymer added in step (1) is 1phr (Phr is the abbreviation of Parts per hundred parts of resin, representing the amount of curcumin polymer added to be formulated in every 100 parts of PA6 / curcumin polymer premix); the temperature of the twin-screw extruder from the feed port to the die head in step (1) is set to 130°C, 160°C, 190°C, 215°C, 223°C, 223°C, 225°C, 230°C, 220°C, the main screw speed is 250±50rpm, the feed screw speed is 20±5rpm, and the granulator speed is 120±50rpm. The temperature of the melt spinning machine from the feed port to the die head in step (2) is set to 180°C, 223°C, 223°C, 225°C.
[0034] Mechanical property test: The fluorescent fiber obtained in step (2) was subjected to mechanical property test with reference to GB / T 14344-2008 "Chemical fiber. Test method for tensile properties of filaments". The breaking strength and breaking elongation of Example 2 (fluorescent nylon 6 fiber) are shown in Table 1 below.
[0035] Example 3
[0036] Preparation of fluorescent nylon 6 fiber:
[0037] Step (1): The curcumin polymer and PA6 prepared in Example 1 are used as raw materials. PA6 is placed in a rotary drum drying oven for drying. The dried PA6 and curcumin polymer are mixed uniformly in a certain ratio, put into a twin-screw extruder, melt-extruded under certain temperature, feed speed, and main screw speed, and granulated by a granulator to obtain fluorescent masterbatch.
[0038] Step (2): The fluorescent masterbatch and spinning chips obtained in step (1) are used as raw materials, and after drying, they are put into a melt spinning machine in a certain proportion, and are drawn into filaments at a certain temperature, screw speed, and drawing speed to obtain fluorescent fibers.
[0039] The drying time described in the above step (1) is 10h, and the moisture content after drying is ≤100ppm; the curcumin polymer added in Example 1 described in step (1) is 2phr; the temperature of the twin-screw extruder from the feed port to the die head is set to 130℃, 160℃, 190℃, 218℃, 225℃, 225℃, 228℃, 232℃, 220℃, the main screw speed is 250±50rpm, the feed screw speed is 20±5rpm, and the granulator speed is 120±50rpm. The temperature of the melt spinning machine from the feed port to the die head described in step (2) is set to 185℃, 222℃, 223℃, 223℃.
[0040] Mechanical property test: The fluorescent fiber obtained in step (2) was subjected to mechanical property test with reference to GB / T 14344-2008 "Chemical fiber. Test method for tensile properties of filaments". The breaking strength and breaking elongation of Example 3 (fluorescent nylon 6 fiber) are shown in Table 1 below.
[0041] Example 4
[0042] Preparation of fluorescent polypropylene fiber:
[0043] Step (1): The curcumin polymer and PP prepared in Example 1 are used as raw materials. The PP is placed in a drum drying oven for drying. The dried PP and the curcumin polymer prepared in Example 1 are mixed uniformly in a certain ratio, put into a twin-screw extruder, melt-extruded under certain temperature, feed speed, and main screw speed, and granulated by a granulator to obtain a fluorescent masterbatch.
[0044] Step (2): The fluorescent masterbatch and spinning chips obtained in step (1) are used as raw materials, and after drying, they are put into a melt spinning machine in a certain proportion, and are drawn into filaments at a certain temperature, screw speed, and drawing speed to obtain fluorescent fibers.
[0045] The drying time described in the above step (1) is 10h, and the moisture content after drying is ≤100ppm; the curcumin polymer added in Example 1 described in step (1) is 1phr; the temperature of the twin-screw extruder from the feed port to the die head is set to 90°C, 110°C, 125°C, 145°C, 153°C, 155°C, 155°C, 160°C, 160°C, the main screw speed is 250±50rpm, the feed screw speed is 18±5rpm, and the granulator speed is 130±50rpm. The temperature of the melt spinning machine from the feed port to the die head described in step (2) is set to 120°C, 155°C, 155°C, and 160°C.
[0046] Mechanical property test: The fluorescent fiber obtained in step (2) was subjected to mechanical property test with reference to GB / T 14344-2008 "Chemical fiber. Test method for tensile properties of filaments". The breaking strength and breaking elongation of Example 4 (fluorescent polypropylene fiber) are shown in Table 1 below.
[0047] Example 5
[0048] Preparation of fluorescent polypropylene fiber:
[0049] Step (1): The curcumin polymer and PP prepared in Example 1 are used as raw materials. The PP is placed in a drum drying oven for drying. The dried PP and the curcumin polymer prepared in Example 1 are mixed uniformly in a certain ratio, put into a twin-screw extruder, melt-extruded under certain temperature, feed speed, and main screw speed, and granulated by a granulator to obtain a fluorescent masterbatch.
[0050] Step (2): The fluorescent masterbatch and spinning chips obtained in step (1) are used as raw materials, and after drying, they are put into a melt spinning machine in a certain proportion, and are drawn into filaments at a certain temperature, screw speed, and drawing speed to obtain fluorescent fibers.
[0051] The drying time described in the above step (1) is 10h, and the moisture content after drying is ≤100ppm; the curcumin polymer added in Example 1 described in step (1) is 2phr; the temperature of the twin-screw extruder from the feed port to the die head is set to 90℃, 110℃, 125℃, 140℃, 155℃, 157℃, 157℃, 165℃, 160℃, the main screw speed is 250±50rpm, the feed screw speed is 18±5rpm, and the granulator speed is 130±50rpm. The temperature of the melt spinning machine from the feed port to the die head described in step (2) is set to 120℃, 158℃, 158℃, 160℃.
[0052] Mechanical property test: The fluorescent fiber obtained in step (2) was subjected to mechanical property test with reference to GB / T 14344-2008 "Chemical fiber. Test method for tensile properties of filaments". The breaking strength and breaking elongation of Example 5 (fluorescent polypropylene fiber) are shown in Table 1 below.
[0053] Table 1
[0054]
Claims
1. A curcumin polymer synthesized from a natural extract curcumin, characterized in that: The structural formula of the curcumin polymer is: 。 2. The curcumin polymer according to claim 1, characterized in that: Under irradiation with a 365nm ultraviolet lamp, the curcumin polymer emits yellow-green fluorescence in a solid state with an emission wavelength of 475-625nm, and does not emit light in a dilute solution state, having typical aggregation-induced emission properties.
3. The curcumin polymer according to claim 1, characterized in that: Curcumin polymer has good antibacterial properties.
4. The method for preparing the curcumin polymer according to any one of claims 1 to 3, characterized in that: The specific steps include: In a Schlenk tube filled with CsCO3, curcumin and 1,3-di(bromomethyl)benzene are added and dissolved in THF to obtain a mixed solution, and the mixed solution is placed in air at 70°C and slowly stirred for reaction for 24 hours. After 24 hours, the reaction solution is cooled to room temperature; CsCO3 in the reaction solution is filtered to obtain a mixed solution, and the mixed solution is concentrated under reduced pressure to obtain a product precipitate; the product is precipitated in excess petroleum ether, filtered and vacuum dried to obtain a yellow solid powder, i.e., curcumin polymer.
5. Application of the curcumin polymer according to any one of claims 1 to 3 or the method for preparing the curcumin polymer according to claim 4 in the preparation of fluorescent fibers, the steps of which are as follows: Step 1: uniformly mixing the curcumin polymer described in any one of claims 1 to 3 or the curcumin polymer prepared by the preparation method described in claim 4 with a resin matrix in a certain ratio, putting the mixture into a twin-screw extruder, melt-extrude the mixture under certain temperature, feed speed, and main screw speed, and granulate the mixture through a granulator to obtain a fluorescent masterbatch; Step 2: The fluorescent masterbatch and spinning chips obtained in step 1 are used as raw materials, and after drying, they are put into a melt spinning machine in a certain proportion, and are drawn into filaments at a certain temperature, screw speed, and drawing speed to obtain fluorescent fibers.
6. The use according to claim 5, characterized in that: In step 1, the mixing ratio of curcumin polymer to resin matrix is 0.2-10 phr, the type of resin matrix is selected from one of PA6, PP, and PET, the temperature of the twin-screw extruder is 80-280 ° C, the main screw speed is 150-250 rpm, the feeding screw speed is 10-40 rpm, and the granulator speed is 50-200 rpm. In step 2, the temperature of the melt spinning machine is 120-280 ° C.
7. The fluorescent fiber obtained by the preparation method of claim 5, characterized in that: The fiber fineness of the fluorescent fiber is in the range of 0.20-0.40 mm, and it emits yellow fluorescence under a 365nm ultraviolet lamp, and the fluorescent fiber is evenly distributed.