Functional fiber spinning preparation method based on macroscopic preparation of organic micro-nano photo-thermal eutectic material
Selecting suitable organic small molecules and polymers through wet spinning technology can realize the domain self-assembly and macro-preparation of organic photothermal eutectic materials, solving the problems of low yield and inability to industrialize organic micro-nano photothermal eutectic materials in the prior art, and achieving continuous and macro-preparation.
Patent Information
- Application Number
- CN202510373941.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-08-19
- Filing Date
- 2025-03-27
- Publication Date
- 2025-06-27
AI Technical Summary
The prior art is difficult to realize the continuous macro preparation of organic micro-nano-photothermal eutectic materials, resulting in extremely low output and inability to produce industrially.
Wet spinning technology is adopted, by selecting fused ring-based small molecules with π-conjugated structure and organic conjugated small molecules with cyano groups, benzenequinone and other structures as electron donors and acceptors, combined with polymers, magnetic stirring is carried out at room temperature to form a wet spinning solution, and by regulating spinning technical parameters, the limited domain self-assembly and macro-preparation of organic photothermal eutectic materials is achieved.
It has successfully overcome the difficulty of continuous macro-preparation of organic micro-nano crystals, achieved continuous and macro-preparation of organic near-infrared photothermal eutectic materials, and solved the problems of low yield and difficult industrial production.
Smart Images
Figure CN120210983A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of functional fibers, and in particular relates to a method for preparing functional fibers by spinning based on macro-scale preparation of organic micro-nano photothermal eutectic materials. Background Art
[0002] Organic photothermal materials have high photothermal conversion efficiency, and have the characteristics of tailorable molecular structure, low-temperature solution processing and adjustable physical and chemical properties. These characteristics make them of great scientific research and commercial application value in the field of low-cost, thin and flexible optoelectronic devices. However, the design of organic photothermal materials based on single-molecule systems is complex and the preparation is cumbersome, which brings challenges to practical applications (see literature: Adv.sci.2023,10,2206830). Organic eutectics can retain the properties of a single component and obtain novel optoelectronic properties due to their unique molecular arrangement and synergistic effects between multiple components (see literature: Angew.Chem.Int.Ed.2022,61,e202202571). However, the yield of organic photothermal eutectic materials with high crystallinity and regular morphology is extremely low. Currently, only milligram-level synthesis can be achieved, and industrial continuous large-scale preparation is difficult (see literature: Adv.Mater.2019,31,1902328). Therefore, it is urgent to design and develop methods for large-scale preparation of organic near-infrared photothermal eutectic materials. Summary of the invention
[0003] In order to solve the above-mentioned technical problems, this application provides the following technical solutions:
[0004] The present invention proposes a continuous, macro-quantitative preparation method and application of organic near-infrared photothermal eutectic materials. In view of the limitations of the existing technology, wet spinning is used to achieve the transformation of organic photothermal materials from micro to macro, successfully overcoming the difficulty of continuous and macro-quantitative preparation of organic micro-nano crystals.
[0005] The present invention provides a method for preparing functional fibers by spinning based on macro-scale preparation of organic micro-nano photothermal eutectic materials, comprising the following steps:
[0006] Selecting fused ring small molecules with π conjugated structure, tetrathiafulvalene and its derivatives, benzidine molecules as electron donors, organic conjugated small molecules with cyano, benzoquinone, phthalic anhydride structure as electron acceptors, accurately weighing the electron donor and acceptor at a molar ratio of 1:1 to 1:4, adding them to a suitable organic solvent and mixing them thoroughly to obtain an electron donor and acceptor stock solution with a concentration of 0.1 mmol / L to 10 mmol / L, then adding 15 to 25 wt% of polymer, treating at room temperature (25±5°C) under magnetic stirring until the polyurethane is completely dissolved, and obtaining a wet spinning solution;
[0007] Preferably, the spinning solution is subjected to wet spinning. By controlling the wet spinning technical parameters: draw ratio of 1:0.1 to 1:10, extrusion speed of 1 to 20 mL / h, needle hole diameter of 14 to 20 G, and coagulation bath temperature of 5 to 50 °C, the confined self-assembly and mass preparation of the organic photothermal eutectic material during the fiber forming process are realized, and a new type of heat storage fiber based on the organic photothermal eutectic material is constructed.
[0008] Preferably, the electron donor in the present invention is selected from N,N-dimethyl-2-naphthylamine, naphthalene, benzo[c]phenanthrene, benzo[a]phenanthrene, phenanthrene, coronene, triphenylene, benzo(a)anthracene, 7,12-dimethylbenzo[a]anthracene, anthracene, 1,12-benzoperylene, perylene, dibenzo(a,h)pyrene, benzo[E]pyrene, benzo[a]pyrene, pyrene, dibenzothiophene, benzo[1,2-b:4,5-b']dithiophene, benzonaphtho(1,2-D)thiazole, tetrathiafulvalene, thiafulvalene benzoic acid, tetrathiafulvalene tetraphenylmethanal, dibenzotetrathiafulvalene, benzidine, 3,3',5,5'-tetramethylbenzidine, N,N,N",N'-tetramethylbenzidine, 4,4'-diiodo-3,3'-dimethylbiphenyl, 3,3'-diaminobenzidine or 4,4'-diamino-3,3'-dimethylbiphenyl.
[0009] Preferably, the electron acceptor in the present invention is selected from o-tetrachlorobenzoquinone, tetrachlorobenzoquinone, tetrafluoro-p-benzoquinone, tetrabromo-p-benzoquinone, tetraiodobenzoquinone, 1,2,4,5-tetracyanobenzene, 7,7,8,8-tetracyanoquinodimethane, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyano-p-xylene, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoroterephthalonitrile, tetrachloroisophthalonitrile, 4,5-dichlorophthalonitrile, 3,4,5,6-tetrafluorophthalonitrile, phthalic anhydride, tetrabromophthalic anhydride, 3,4,5,6-tetrafluorophthalic anhydride or tetrachlorophthalic anhydride.
[0010] Preferably, the organic solvent is one or a mixed solution of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, dichloromethane, tetrahydrofuran and chloroform.
[0011] Preferably, in the spinning solution, the polymer is selected from one or a mixture of polyester-based polyurethane, polyether-based polyurethane, thermoplastic polyurethane, waterborne polyurethane, nylon, acrylic fiber, cellulose acetate and polyamide.
[0012] Preferably, in the mass preparation method, the coagulation bath is selected from one or a mixed solvent of water, alcohols, acetonitrile,
[0013] Preferably, the coagulation bath further contains an acidic or basic additive.
[0014] Furthermore, the acidic additive selected for the coagulation bath in the present invention is one or a mixture of sulfuric acid, sodium sulfate, and hydrochloric acid.
[0015] Furthermore, the basic additive selected for the coagulation bath in the present invention is one or a mixture of sodium hydroxide, potassium hydroxide, and ammonia water.
[0016] In the present invention, small aromatic molecules with a π-conjugated molecular structure, tetrathiafulvalene and its derivatives, and benzidine molecules are selected as electron donors from the aspects of molecular structure and energy level matching, and organic conjugated small molecules with structures such as cyano groups, benzoquinones, and phthalic anhydrides are used as electron acceptors. Through a spinning chemical strategy, in-situ growth and continuous preparation of organic near-infrared photothermal eutectic materials are realized. During the wet spinning process, when the polyurethane substrate material contacts the water in the coagulation bath, fibers are cross-linked. At the same time, the donor and acceptor raw materials in-situ grow into organic micro-nano eutectic materials on the surface and inside of the fibers under the drive of charge transfer forces. As the fibers are continuously formed and collected by the fiber collector, the organic micro-nano eutectic materials are also continuously prepared and produced.
[0017] The technical solution of the present invention has the following advantages compared with the prior art:
[0018] (1) Based on eutectic engineering, the present invention uses organic donor and acceptor materials and, through a wet spinning process, in-situ prepares organic near-infrared photothermal eutectic materials inside and on the surface of polyurethane fibers, avoiding the cumbersome and complex molecular design and synthesis processes.
[0019] (2) The present invention provides a continuous and large-scale preparation method for organic near-infrared photothermal eutectic materials, overcoming the difficulties of low yield of organic micro-nano eutectics and inability to industrialize production. Description of the Drawings
[0020] Figure 1 It is the molecular formula set of the electron donor described in the present invention.
[0021] Figure 2 It is the molecular formula set of the electron acceptor described in the present invention.
[0022] Figure 3 It is the actual photo and SEM image of the NDA-CA organic photothermal eutectic fiber loaded provided in Example 1 of the present invention.
[0023] Figure 4 It is the SEM image of the photothermal eutectic material NDA-CA loaded on the fiber provided in Example 1 of the present invention.
[0024] Figure 5 It is the ultraviolet-visible-near-infrared absorption spectrum of polyurethane, NDA-CA eutectic, and NDA-CA@polyurethane provided in Example 1 of the present invention.
[0025] Figure 6 For Example 1 of the present invention, at a power density of 0.301 W / cm 2 The photothermal performance test diagrams of polyurethane, NDA-CA eutectic, and NDA-CA@polyurethane.
[0026] Figure 7 For the NDA-CA eutectic provided in Example 1 of the present invention at 0.301 W / cm 2 The photothermal stability test diagram (a) and the photothermal stability test diagram (b) of NDA-CA@polyurethane at 0.301 W / cm 2 Detailed implementation mode
[0027] The present invention will be further described below in conjunction with the figures and specific embodiments, so that those skilled in the art can better understand the present invention and be able to implement it, but the embodiments cited do not limit the present invention.
[0028] Example 1
[0029] 0.085 g of N,N-dimethyl-2-naphthylamine (NDA) and 0.125 g of o-chloranil (CA) were added to 9 mL of a mixed solvent of N,N-dimethylformamide and acetonitrile (volume ratio 6:3), and then 1.25 g of polyurethane (PU) was added. The mixture was magnetically stirred until the PU was completely dissolved to obtain a spinning solution.
[0030] The spinning solution was sucked into a disposable syringe and fixed on a syringe pump for wet spinning. Among them, the needle size was 18G, the feeding speed was 6 mL / h, the draw ratio was 1:1.5, the temperature was 20 °C, and the humidity was 45%. It was solidified and formed in a deionized water coagulation bath to obtain polyurethane fibers loaded with NDA-CA eutectic material (NDA-CA@PU).
[0031] The NDA-CA@PU fibers were further ultrasonically exfoliated to obtain pure NDA-CA organic micro-nano crystal materials. The steps were as follows: 300 mL of deionized water was added to a beaker, and then 10 g of fibers loaded with NDA-CA organic micro-nano crystal materials were completely immersed therein. The NDA-CA organic micro-nano crystals grown on the fibers were exfoliated under ultrasonic conditions at 20 °C and 25 kHz; after 1 h of ultrasonic treatment, centrifugation was carried out at 7000 r / min, the supernatant was removed, and the precipitate was dried to obtain pure NDA-CA organic micro-nano crystal materials.
[0032] Example 2
[0033] Dissolve 0.085 g of N,N-dimethyl-2-naphthylamine (NDA) and 0.125 g of o-chloranil (CA) in 8 mL of a mixed solvent of N,N-dimethylformamide and acetonitrile (volume ratio 5:3), then add 1.2 g of polyurethane (PU), and stir magnetically until the PU is completely dissolved to obtain a spinning solution.
[0034] Draw the spinning solution into a disposable syringe, fix it on a syringe pump for wet spinning. Among them, the needle size is 18G, the pushing speed is 3 mL / h, the draw ratio is 1:5, the temperature is 25 °C, and the humidity is 45%. It is solidified and formed in a deionized water coagulation bath to obtain polyurethane fibers loaded with NDA-CA eutectic materials (NDA-CA@PU).
[0035] Further obtain pure NDA-CA organic micro-nano crystal materials by ultrasonic exfoliation of NDA-CA@PU fibers. The steps are as follows: Add 300 mL of deionized water to a beaker, then completely immerse 10 g of fibers loaded with NDA-CA organic micro-nano crystal materials in it, and exfoliate the NDA-CA organic micro-nano crystals grown on the fibers under ultrasonic conditions of 20 °C and 25 kHz; after ultrasonic treatment for 1 h, centrifuge at 7000 r / min, remove the supernatant and dry the precipitate to obtain pure NDA-CA organic micro-nano crystal materials.
[0036] Example 3
[0037] Dissolve 0.085 g of N,N-dimethyl-2-naphthylamine (NDA) and 0.125 g of o-chloranil (CA) in 9 mL of a mixed solvent of N,N-dimethylformamide and acetonitrile (volume ratio 6:3), then add 1.25 g of polyurethane (PU), and stir magnetically until the PU is completely dissolved to obtain a spinning solution.
[0038] Draw the spinning solution into a disposable syringe, fix it on a syringe pump for wet spinning. Among them, the needle size is 18G, the pushing speed is 15 mL / h, the draw ratio is 1:3, the temperature is 15 °C, and the humidity is 40%. It is solidified and formed in a deionized water coagulation bath to obtain polyurethane fibers loaded with NDA-CA eutectic materials (NDA-CA@TPU).
[0039] Further obtain pure NDA-CA organic micro-nano crystal materials by ultrasonic exfoliation of NDA-CA@PU fibers. The steps are as follows: Add 300 mL of deionized water to a beaker, then completely immerse 15 g of fibers loaded with NDA-CA organic micro-nano crystal materials in it, and exfoliate the NDA-CA organic micro-nano crystals grown on the fibers under ultrasonic conditions of 25 °C and 25 kHz; after ultrasonic treatment for 1 h, centrifuge at 6500 r / min, remove the supernatant and dry the precipitate to obtain pure NDA-CA organic micro-nano crystal materials.
[0040] Example 4
[0041] 0.085 g of N,N-dimethyl-2-naphthylamine (NDA) and 0.125 g of o-chloranil (CA) were added to 8 mL of a mixed solvent of N,N-dimethylformamide and acetonitrile (volume ratio 5:3), and then 1.2 g of polyurethane (PU) was added. The mixture was stirred magnetically until the PU was completely dissolved to obtain a spinning solution.
[0042] The spinning solution was drawn into a disposable syringe and fixed on a syringe pump for wet spinning. Among them, the needle size was 18G, the feeding speed was 10 mL / h, the draw ratio was 1:2, the temperature was 20 °C, and the humidity was 40%. It was solidified and formed in a deionized water coagulation bath to obtain polyurethane fibers loaded with NDA-CA eutectic materials (NDA-CA@PU).
[0043] The NDA-CA@PU fibers were further ultrasonically exfoliated to obtain pure NDA-CA organic micro-nano crystal materials. The steps were as follows: 300 mL of deionized water was added to a beaker, and then 15 g of fibers loaded with NDA-CA organic micro-nano crystal materials were completely immersed therein. The NDA-CA organic micro-nano crystals grown on the fibers were exfoliated under ultrasonic conditions at 25 °C and 25 kHz; after 1 h of ultrasonic treatment, centrifugation was carried out at 7000 r / min, the supernatant was removed, and the precipitate was dried to obtain pure NDA-CA organic micro-nano crystal materials.
[0044] Example 5
[0045] 0.085 g of N,N-dimethyl-2-naphthylamine (NDA) and 0.125 g of o-chloranil (CA) were added to 7 mL of a mixed solvent of N,N-dimethylformamide and acetonitrile (volume ratio 4:3), and then 1.25 g of polyurethane (PU) was added. The mixture was stirred magnetically until the PU was completely dissolved to obtain a spinning solution.
[0046] The spinning solution was drawn into a disposable syringe and fixed on a syringe pump for wet spinning. Among them, the needle size was 18G, the feeding speed was 20 mL / h, the draw ratio was 1:1, the temperature was 25 °C, and the humidity was 45%. It was solidified and formed in a deionized water coagulation bath to obtain polyurethane fibers loaded with NDA-CA eutectic materials (NDA-CA@PU).
[0047] The NDA-CA@PU fibers were further ultrasonically exfoliated to obtain pure NDA-CA organic micro-nano crystal materials. The steps are as follows: Add 300 mL of deionized water into a beaker, and then completely immerse 10 g of the fibers loaded with NDA-CA organic micro-nano crystal materials therein. Under the ultrasonic conditions of 25 °C and 25 kHz, exfoliate the NDA-CA organic micro-nano crystals grown on the fibers; after ultrasonic treatment for 1 h, perform centrifugation at 7000 r / min, remove the supernatant and dry the precipitate to obtain pure NDA-CA organic micro-nano crystal materials.
[0048] Effect evaluation 1
[0049] See Figure 1 , which is the molecular formula set of the electron donor described in the present invention and is a polycyclic small molecule with a π-conjugated structure, tetrathiafulvalene and its derivatives, and benzidine molecules.
[0050] See Figure 2 , which is the molecular formula set of the electron acceptor described in the present invention and is an organic conjugated small molecule with structures such as cyano, benzoquinone, and phthalic anhydride.
[0051] See Figure 3 , which are the actual photos of the polyurethane fibers (NDA-CA@PU) loaded with NDA-CA eutectic materials obtained by wet spinning provided in Example 1 of the present invention and the SEM images of the NDA-CA@PU fibers. It can be seen that the fibers are uniform in thickness and have a diameter of about 400 μm.
[0052] See Figure 4 , which is the SEM image of the NDA-CA organic micro-nano crystals loaded on the fibers provided in Example 1 of the present invention; as can be seen from Figure 4 , the crystals are located on the surface and inside of the fibers, are evenly distributed, and have a length of 5-20 μm, which proves that the NDA-CA organic micro-nano crystals can be successfully prepared in large quantities by wet spinning technology.
[0053] See Figure 5 , which are the ultraviolet-visible-near-infrared absorption spectra of polyurethane, NDA-CA eutectic, and NDA-CA@polyurethane provided in Example 1 of the present invention; compared with pure polyurethane fibers, the absorptions of NDA-CA eutectic and NDA-CA@polyurethane fibers have undergone red shifts and both have reached the near-infrared region.
[0054] See Figure 6 , which is the comparison chart of the photothermal properties of polyurethane, NDA-CA eutectic, and NDA-CA@polyurethane fibers provided in Example 1 of the present invention. At a power density of 0.301 W / cm 2Under the irradiation of an 808 nm laser lamp, the temperature of polyurethane, NDA-CA@polyurethane fiber, and NDA-CA eutectic material can rise from room temperature to 27.8 °C, 78 °C, and 93 °C respectively, fully demonstrating the excellent photothermal performance of the NDA-CA eutectic material prepared by the present invention.
[0055] See Figure 7 , which is the photothermal stability test chart (a) of the NDA-CA eutectic provided in Example 1 of the present invention at 0.301 W / cm 2 , and the photothermal stability test chart (b) of NDA-CA@polyurethane at 0.301 W / cm 2 . The 12 heating and cooling cycle tests at the same power density illustrate that the NDA-CA eutectic and NDA-CA@polyurethane fiber have excellent photothermal performance and photothermal stability, proving the successful large-scale preparation of the organic photothermal eutectic material based on the wet spinning technology.
[0056] Obviously, the above examples are only for illustration purposes and are not intended to limit the implementation methods. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all implementation methods here. The obvious changes or modifications derived therefrom are still within the protection scope of the present invention.
Claims
1. A method for preparing functional fiber spinning based on macro-scale preparation of organic micro-nano photothermal eutectic materials, characterized in that: The steps include: S1: Selecting fused ring small molecules with π conjugated structure, tetrathiafulvalene and its derivatives or benzidine molecules as electron donors, and organic conjugated small molecules with cyano, benzoquinone or phthalic anhydride structure as electron acceptors, weighing the electron donor and the electron acceptor in a molar ratio of 1:1-4, adding them into an organic solvent and mixing them thoroughly to obtain a 0.1mmol / L-10mmol / L electron donor and acceptor stock solution, then adding a polymer with a concentration of 15-25wt%, treating at room temperature and magnetic stirring until the polymer is completely dissolved, and obtaining a wet spinning solution; S2: Wet-spinning the wet spinning solution, and adjusting the wet spinning technical parameters: draft ratio 1: 0.1-10, extrusion speed 1-20mL / h, pinhole aperture 14-20G, coagulation bath temperature 5-50°C, to achieve confined self-assembly and macro-scale preparation of the organic photothermal eutectic material in the fiber forming process, and prepare the functional fiber spinning based on the macro-scale preparation of the organic micro-nano photothermal eutectic material.
2. The preparation method according to claim 1, characterized in that The electron donor is selected from N,N-dimethyl-2-naphthylamine, naphthalene, benzo[c]phenanthrene, benzo[a]phenanthrene, phenanthrene, coronene, triphenylene, benzo(a)anthracene, 7,12-dimethylbenzo[a]anthracene, Anthracene, 1,12-benzoperylene, perylene, dibenzo(a,h)pyrene, benzo[E]pyrene, benzo[a]pyrene, pyrene, dibenzothiophene, benzo[1,2-b:4,5-bˋ]dithiophene, benzonaphthalene(1,2-D)thiazole, tetrathiafulvalene, thiafulvalene benzoic acid, tetrathiafulvalene tetrabenzaldehyde, dibenzotetrathiafulvalene, benzidine, 3,3',5,5'-tetramethylbenzidine, N,N,N",N'-tetramethylbenzidine, 4,4'-diiodo-3,3'-dimethylbiphenyl, 3,3'-diaminobenzidine or 4,4'-diamino-3,3'-dimethylbiphenyl.
3. The preparation method according to claim 1, characterized in that: The electron acceptor is selected from o-tetrachlorobenzoquinone, tetrachlorobenzoquinone, tetrafluoro-p-benzoquinone, tetrabromo-p-benzoquinone, tetraiodobenzoquinone, 1,2,4,5-tetracyanobenzene, 7,7,8,8-tetracyanobenzoquinodimethane, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 2,5-difluoro-7,7,8,8-tetracyanobenzoquinodimethane, 2,3,5,6-tetrafluoroterephthalonitrile, tetrachloroisophthalonitrile, 4,5-dichlorophthalonitrile, 3,4,5,6-tetrafluorophthalonitrile, phthalic anhydride, tetrabromophthalic anhydride, 3,4,5,6-tetrafluorophthalic anhydride or tetrachlorophthalic anhydride.
4. The preparation method according to claim 1, characterized in that: The organic solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, dichloromethane, tetrahydrofuran and chloroform.
5. The preparation method according to claim 1, characterized in that: In the wet spinning solution, the polymer is selected from one or more of polyester polyurethane, polyether polyurethane, thermoplastic polyurethane, waterborne polyurethane, nylon, acrylic fiber, cellulose acetate and nylon.
6. The preparation method according to claim 1, characterized in that: The coagulation bath is selected from one of water, alcohols and acetonitrile or a mixed solvent thereof.
7. The preparation method according to claim 1, characterized in that: The coagulation bath further contains an acidic additive or an alkaline additive.
8. The preparation method according to claim 7, characterized in that: The acidic additive is selected from one or more mixtures of sulfuric acid, sodium sulfate and hydrochloric acid.
9. The preparation method according to claim 7, characterized in that: The alkaline additive is selected from one or more mixtures of sodium hydroxide, potassium hydroxide and ammonia water.