Temperature response dynamic luminescent fiber and preparation method and application thereof

Abstract

The invention provides a temperature response dynamic luminescent fiber as well as a preparation method and application thereof, and belongs to the technical field of automotive interior materials. A polyacrylonitrile spinning solution is mixed with a rare earth long afterglow luminescent material and a temperature response color-changing pigment to prepare a spinning solution, and the luminescent fiber is prepared through a wet spinning process. The fiber prepared by the invention can be almost perfectly matched and fused with a 3D irregular structure in an automobile, has the air permeability and moisture permeability of a fabric, and forms point-to-surface atmosphere luminescence; and after collision, scattering and ejection are not prone to occurring, and safety performance is high. The fiber not only has temperature color response, but also can realize light energy absorption-storage-release, and can be recycled. In addition, the prepared fiber has the advantages of being high in temperature discoloration response speed, good in fatigue resistance, high in fluorescent brightness, long in afterglow time and the like.

Description

Technical Field

[0001] This invention relates to the field of automotive interior materials technology, and in particular to a temperature-responsive dynamic luminescent fiber, its preparation method, and its application. Background Technology

[0002] As cars evolve into a third living space, their ambiance and level of emotional interaction have become crucial factors for consumers when purchasing vehicles. More and more consumers are paying attention not only to the quality of the interior but also to the creation of a specific atmosphere. Currently, ambient lighting, as a product that can both decorate and enhance the atmosphere, is playing an increasingly important role in automotive interior spaces.

[0003] With the advancement of technology and economic development, traditional car interiors can no longer meet people's aesthetic requirements and expectations for personalization. Car ambient lighting based on LED light strips or PMMA light guide plates not only has high energy consumption, but also has the following problems: (1) Based on hard planar materials, it is difficult to effectively combine with the curved 3D structure inside the car, the light-emitting area is limited, and the space for aesthetic design is small; (2) It is easy to break off and burn in the event of a collision, causing secondary injuries to the driver and passengers, and the safety factor is low. Moreover, traditional car interior materials based on ambient light strips are difficult to effectively combine with the curved 3D structure inside the car, the light-emitting area is limited, not only resulting in low collision safety, but also failing to meet people's aesthetic requirements and expectations for personalization of car interiors.

[0004] Therefore, overcoming the drawbacks of traditional automotive interior ambient lighting, such as its rigidity and low safety, and seeking a safe, flexible, and convenient method to create an ambiance in automotive interiors is an urgent problem to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide a temperature-responsive dynamic luminescent fiber, its preparation method, and its application. The prepared fiber can be almost perfectly adapted and integrated with the 3D irregular structure inside the car, forming an ambient light emission from point to surface. Moreover, it is not easy to scatter and eject after a collision, and has high safety performance, overcoming the drawbacks of traditional car interior ambient lights that are hard and have low safety. It is also safe, flexible, and convenient.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing temperature-responsive dynamic light-emitting fibers, comprising the following steps: Polyacrylonitrile is mixed with a dispersant to obtain PAN nascent spinning solution; The PAN nascent spinning solution is mixed with rare earth long afterglow luminescent material and temperature-responsive color-changing pigment, and defoaming treatment is performed to obtain temperature-responsive dynamic luminescent PAN spinning solution. The rare earth long-afterglow luminescent material includes the red long-afterglow luminescent material CaTiO3:Pr. 3+ and green long afterglow luminescent material MgAl2O4:Ce 3+ The temperature-responsive color-changing pigment is a thermochromic material composed of leuco dye microcapsules. After wet spinning the temperature-responsive dynamic luminescent PAN spinning solution, it is dried to obtain temperature-responsive dynamic luminescent fibers.

[0007] Preferably, the dispersant comprises one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and ethylene carbonate.

[0008] Preferably, the concentration of polyacrylonitrile in the PAN primary spinning solution is 40~60wt%.

[0009] Preferably, the green long afterglow luminescent material MgAl2O4:Ce 3+ And red long afterglow luminescent material CaTiO3:Pr 3 + The mass ratio is 0.5~1:1.

[0010] Preferably, the leuco dye microcapsule thermochromic material turns green upon temperature change.

[0011] Preferably, the mass ratio of the temperature-responsive color-changing pigment to the rare-earth long-afterglow luminescent material is 0.04~0.1:1; and the mass ratio of the total mass of the temperature-responsive color-changing pigment and the rare-earth long-afterglow luminescent material to the mass of the PAN primary spinning solution is 0.02~0.06:1.

[0012] Preferably, the defoaming treatment is performed at a pressure of 300-600 Torr for 5-10 minutes.

[0013] Preferably, the conditions for wet spinning include: a feed rate of 4-8 mm / min; a spinneret diameter of 0.15-0.55 mm; a coagulation bath that is a mixture of organic solvent and water, wherein the mass concentration of the organic solvent in the coagulation bath is 10-30%, and the coagulation bath temperature is 20-50°C; during the wet spinning process, the spinneret is first stretched by 1.5-3 times in the coagulation bath, and then stretched by 2-4 times in the water bath, wherein the water bath temperature is 80-100°C.

[0014] This invention provides temperature-responsive dynamic light-emitting fibers prepared by the preparation method described in the above technical solution.

[0015] This invention provides the application of the temperature-responsive dynamic light-emitting fiber described above in the field of automotive interior ambiance.

[0016] This invention provides a method for preparing temperature-responsive dynamic luminescent fibers. The method involves mixing a polyacrylonitrile spinning solution with a rare-earth long-afterglow luminescent material and a temperature-responsive color-changing pigment to prepare the spinning solution, followed by wet spinning to prepare the luminescent fibers. The fibers prepared by this invention incorporate leuco dye microcapsule thermochromic material and rare-earth long-afterglow luminescent material. In darkness, as the temperature changes, reversible electron transfer occurs between the chromophore and chromogenic molecules within the leuco dye microcapsule thermochromic material, causing a change in the visible light absorption spectrum of the fiber. This leads to selective absorption of the emitted light from the rare-earth luminescent material, resulting in a color change. This synergistic effect causes the fiber to dynamically change its color with temperature, creating a dynamic luminescent effect. Visual warnings (such as luminescence in high-temperature areas) can be provided through intuitive color changes, enabling intelligent environmental control. In terms of safety and human-computer interaction, it can provide heat-sensitive indications. For example, when temperature-controlled luminescent fibers are applied to key contact areas such as seats, steering wheels, or dashboards, the material can alert the driver through color changes or adjustments in luminescence intensity when the surface temperature exceeds a safe threshold, preventing burns from high temperatures or discomfort from low temperatures that could affect driving operation.

[0017] This invention utilizes wet spinning to produce soft fibers that can almost perfectly adapt to and integrate with the irregular 3D structures inside automobiles. Furthermore, these fibers are not easily scattered or ejected after a collision, ensuring high safety. They also possess the breathability and moisture-wicking properties of fabrics, creating an ambient luminescence effect from point to surface. This fiber not only exhibits temperature and color response but also achieves light energy absorption, storage, and release. This is due to the rare-earth materials within the fiber absorbing energy, causing electrons to transition from the ground state to an excited state and maintain this state. After the excitation light source disappears, these excited electrons transition back from the excited state to the ground state, generating long-lasting afterglow luminescence, and are recyclable.

[0018] The preparation process of this invention is simple, and the prepared fibers have advantages such as fast temperature color change response, good fatigue resistance, high fluorescence brightness, and long afterglow time.

[0019] The fiber prepared by this invention achieves the integration of environmental perception, information visualization and energy saving through dual intelligent responses of temperature and optics, showing broad prospects in fields such as smart textiles, safety protection and medical monitoring, and providing people with more convenient and richer living conditions. Attached Figure Description

[0020] Figure 1 Infrared spectrum of the temperature-responsive dynamic luminescent fiber prepared in Example 1; Figure 2 CIE1931 color coordinates of the temperature-responsive dynamic luminescent fiber prepared in Example 1 before and after color change; Figure 3 Reflectance curves of the temperature-responsive dynamic luminescent fiber prepared in Example 1 before and after color change; Figure 4 The afterglow curve of the temperature-responsive dynamic light-emitting fiber prepared in Example 1; Figure 5 The initial brightness of the afterglow after multiple energy absorption and release of the temperature-responsive dynamic luminescent fiber prepared in Example 1; Figure 6 The images show the temperature-responsive dynamic light-emitting fiber prepared in Example 1 at low and high temperatures in the dark. Detailed Implementation

[0021] In this invention, unless otherwise specified, the raw materials or reagents required for preparation are all commercially available products well known to those skilled in the art.

[0022] This invention provides a method for preparing temperature-responsive dynamic light-emitting fibers, comprising the following steps: Polyacrylonitrile is mixed with a dispersant to obtain PAN nascent spinning solution; The PAN nascent spinning solution is mixed with rare earth long afterglow luminescent material and temperature-responsive color-changing pigment, and defoaming treatment is performed to obtain temperature-responsive dynamic luminescent PAN spinning solution. The rare earth long-afterglow luminescent material includes the red long-afterglow luminescent material CaTiO3:Pr. 3+ and green long afterglow luminescent material MgAl2O4:Ce 3+ The temperature-responsive color-changing pigment is a thermochromic material composed of leuco dye microcapsules. After wet spinning the temperature-responsive dynamic luminescent PAN spinning solution, it is dried to obtain temperature-responsive dynamic luminescent fibers.

[0023] In this invention, the weight-average molecular weight (Mw) of the polyacrylonitrile is preferably 100,000 to 500,000, and more preferably 150,000 to 300,000.

[0024] In this invention, the dispersant preferably includes one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and ethylene carbonate; when the dispersant is two or more of the above, this invention does not have a special limitation on the ratio of different types of dispersants, and any ratio is acceptable.

[0025] In this invention, the concentration of polyacrylonitrile in the PAN primary spinning solution is preferably 40-60 wt%, more preferably 53-55 wt%.

[0026] In this invention, the rare earth long-afterglow luminescent material includes the red long-afterglow luminescent material CaTiO3:Pr. 3+ and green long afterglow luminescent material MgAl2O4:Ce 3+ The green long-afterglow luminescent material MgAl2O4:Ce 3+And red long afterglow luminescent material CaTiO3:Pr 3+ The preferred mass ratio is 0.5 to 1:1, and more preferably 0.5 to 0.8:1.

[0027] The present invention does not have any special limitation on the source of the rare earth long afterglow luminescent material, and it can be prepared according to methods well known in the art.

[0028] In this invention, the thermochromic material of the leuco dye microcapsule was purchased from Dongguan Qiansebian New Materials Co., Ltd., and is a temperature-sensitive green powder (changing from white to green at 38°C). Its color-changing mechanism is the reversible electron transfer between the chromogenic agent and the chromogenic agent molecules.

[0029] In this invention, the mass ratio of the temperature-responsive color-changing pigment to the rare-earth long-afterglow luminescent material is preferably 0.04~0.1:1, more preferably 0.04~0.08:1, and even more preferably 0.04~0.05:1; the mass ratio of the total mass of the temperature-responsive color-changing pigment and the rare-earth long-afterglow luminescent material to the mass of the PAN nascent spinning solution is preferably 0.02~0.06:1, more preferably 0.03~0.05:1, and even more preferably 0.04:1.

[0030] In this invention, the defoaming treatment pressure is preferably 300-600 Torr, more preferably 500-600 Torr, and the time is preferably 5-10 min, more preferably 5-8 min. Preferably, the mixture obtained by mixing PAN nascent spinning solution with rare earth long-afterglow luminescent material and temperature-responsive color-changing pigment is placed in a vacuum defoaming machine for defoaming treatment to remove air bubbles from the spinning solution.

[0031] In this invention, the preferred conditions for wet spinning include: a feed rate of 4-8 mm / min, more preferably 5-6 mm / min; and a spinneret diameter of 0.15-0.55 mm, more preferably 0.5-0.55 mm.

[0032] In this invention, the coagulation bath used in the wet spinning is preferably a mixture of organic solvent and water, the mass concentration of the organic solvent in the coagulation bath is preferably 10-30%, more preferably 10-20%, and the coagulation bath temperature is preferably 20-50℃, more preferably 20-30℃; the organic solvent is preferably N,N-dimethylformamide (DMF).

[0033] In this invention, during the wet spinning process, the yarn is first stretched 1.5 to 3 times in a coagulation bath by guide rollers, and then stretched 2 to 4 times in a water bath by guide rollers. The temperature of the water bath is preferably 80 to 100°C, and more preferably 80 to 90°C.

[0034] After completing the wet spinning process, the resulting fibers are washed with water in multiple stages to remove the solvent and then dried in hot air. The drying temperature is preferably 50~80℃, more preferably 50~60℃, and the drying time is preferably 60~120 min, more preferably 100~120 min.

[0035] This invention provides temperature-responsive dynamic light-emitting fibers prepared by the preparation method described in the above technical solution.

[0036] This invention provides the application of the temperature-responsive dynamic luminescent fiber described above in the field of automotive interior ambiance. This invention does not impose any particular limitation on the method of application; any method well-known in the art can be used.

[0037] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention. Unless otherwise specified, the experimental methods described in the embodiments of the present invention are conventional methods.

[0038] Unless otherwise specified, the experimental and testing methods described below are conventional methods; unless otherwise specified, the reagents and raw materials described below are commercially available.

[0039] In the following embodiments, the green long-afterglow luminescent material MgAl2O4:Ce 3+ The preferred preparation method is: Accurately weigh 0.95 mol magnesium oxide, 1 mol aluminum oxide, 0.05 mol cerium oxide, and 0.1 mol boric acid (all analytical grade), add alcohol, ball mill until homogeneous, dry, and then react at 1500℃ for 10 h. After cooling, ball mill again to obtain the green long afterglow material MgAl2O4:Ce. 3+ .

[0040] Red-light long-afterglow luminescent material CaTiO3:Pr 3+ The preferred preparation method is: Accurately weigh 0.998 mol calcium carbonate, 1 mol titanium dioxide, 0.004 mol praseodymium oxide, and 0.1 mol boric acid (all analytical grade), add alcohol, ball mill until homogeneous, dry, and then react at 1300℃ for 3 h. After cooling, ball mill to obtain the red-light long afterglow material CaTiO3:Pr 3+ .

[0041] The green temperature-responsive color-changing pigment is a thermochromic material made of leuco dye microcapsules (changing from white to green at 38℃), sourced from Dongguan Qiansebian New Materials Co., Ltd.

[0042] Example 1

[0043] Take 50 g of polyacrylonitrile powder (weight average molecular weight (Mw) of 150,000) and dissolve it in 100 mL of DMF to obtain a PAN / DMF spinning solution with a concentration of 53 wt%. Take 100 mL (140 g) of PAN / DMF spinning solution and add 2 g of green long afterglow material MgAl2O4:Ce 3+ 4g of red-light long afterglow material CaTiO3:Pr 3+ Mix 0.25g of green temperature-responsive color-changing pigment, stir evenly, place the mixture in a vacuum defoamer, and let it stand for 5 minutes under a negative pressure of 600 Torr to remove bubbles, thus obtaining a temperature-responsive dynamic luminescent PAN spinning solution. The temperature-responsive dynamic luminescent PAN spinning solution was wet-spun using a 10wt% DMF aqueous solution as the coagulation bath, with a feed rate of 5 mm / min, a spinneret diameter of 0.55 mm, and a coagulation bath temperature of 20°C. The fibers were stretched 1.5 times in the coagulation bath by guide rollers, followed by a 2 times stretch in a water bath at 80°C. The resulting fibers were then washed with water in multiple stages to remove the solvent, and dried in hot air at 50°C for 120 min to obtain temperature-responsive dynamic luminescent fibers.

[0044] Example 2

[0045] Take 50 g of polyacrylonitrile powder (weight average molecular weight (Mw) of 150,000) and dissolve it in 100 mL of DMF solution to obtain a PAN / DMF spinning solution with a concentration of 53 wt%. Take 100 mL (140 g) of PAN / DMF spinning solution and add 3 g of green long afterglow material MgAl2O4:Ce 3+ 3g of red-light long afterglow material CaTiO3:Pr 3+ Mix 0.25g of green temperature-responsive color-changing pigment, stir evenly, place the resulting mixture in a vacuum defoamer, and let it stand for 5 minutes under a negative pressure of 600 Torr to remove air bubbles in the spinning solution, thus obtaining a temperature-responsive dynamic luminescent PAN spinning solution. The temperature-responsive dynamic luminescent PAN spinning solution was wet-spun using a 10wt% DMF aqueous solution as the coagulation bath, a feed rate of 5 mm / min, a spinneret diameter of 0.55 mm, and a coagulation bath temperature of 20°C. The fibers were stretched 1.5 times in the coagulation bath by guide rollers, and then stretched 2 times in a water bath at 80°C. After the resulting fibers were washed multiple times to remove the solvent, they were dried in hot air at 50°C for 120 min to obtain temperature-responsive dynamic luminescent fibers.

[0046] Characterization and performance testing Figure 1 The infrared spectrum of the temperature-responsive dynamic luminescent fiber prepared in Example 1; by Figure 1 It can be seen that it is located at 2242cm -1 and 2922 cm -1 These are the stretching vibration peaks of C≡N and CH in PAN. At 1449 cm⁻¹ -1 The characteristic absorption peak at 3316 cm⁻¹ is due to the bending vibration of CH₂. -1 The peak at 2966 cm⁻¹ is caused by the stretching vibration of OH groups. -1 2855 cm -1 and 1463 cm -1 The peak at 1744 cm⁻¹ is due to the stretching vibration of CH in the thermochromic pigment. -1 and 1460cm -1 The peaks at the points are due to the stretching vibrations of C=O and C=C in the thermochromic pigment, indicating that the fiber has been successfully prepared.

[0047] Figure 2 The CIE1931 color coordinates of the temperature-responsive dynamic luminescent fiber prepared in Example 1 before and after color change can be observed. The fiber color coordinates are white at low temperature and green after color change.

[0048] Figure 3 The reflectance curves of the temperature-responsive dynamic luminescent fiber prepared in Example 1 at different temperatures show that the fiber changes color rapidly in response to temperature.

[0049] Figure 4 The afterglow curve of the temperature-responsive dynamic light-emitting fiber prepared in Example 1 shows that the fiber has a relatively long afterglow time.

[0050] Figure 5 The initial afterglow brightness of the temperature-responsive dynamic luminescent fiber prepared in Example 1 after multiple energy absorption and release cycles was measured by placing the fiber in darkness for more than 24 hours to allow it to fully release light energy. The fiber was then excited using a 1000 lx light source, and the initial fluorescence intensity was measured. The initial fluorescence intensity after complete light energy release and subsequent re-excitation was recorded as one cycle. Figure 5 It can be seen that the fiber has high fluorescence intensity, can be reused, and can achieve light energy absorption-storage-release.

[0051] The luminescent fibers prepared in Example 1 were placed on heating stages at different temperatures. Figure 6 The images show the temperature-responsive dynamic luminescent fiber prepared in Example 1 under low and high temperatures in the dark. It can be seen that the color of the fiber changes dynamically at different temperatures. When the temperature is above 38°C, the fiber light color is greener, and when the temperature is below 38°C, the fiber light color turns yellowish-green due to pigment fading.

[0052] 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 method for preparing temperature-responsive dynamic light-emitting fibers, characterized in that, Includes the following steps: Polyacrylonitrile is mixed with a dispersant to obtain PAN nascent spinning solution; The PAN nascent spinning solution is mixed with rare earth long afterglow luminescent material and temperature-responsive color-changing pigment, and defoaming treatment is performed to obtain temperature-responsive dynamic luminescent PAN spinning solution. The rare earth long-afterglow luminescent material includes the red long-afterglow luminescent material CaTiO3:Pr. 3+ and green long afterglow luminescent material MgAl2O4:Ce 3+ The temperature-responsive color-changing pigment is a thermochromic material composed of leuco dye microcapsules. After wet spinning the temperature-responsive dynamic luminescent PAN spinning solution, it is dried to obtain temperature-responsive dynamic luminescent fibers.

2. The preparation method according to claim 1, characterized in that, The dispersant includes one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and ethylene carbonate.

3. The preparation method according to claim 1 or 2, characterized in that, The concentration of polyacrylonitrile in the PAN primary spinning solution is 40~60wt%.

4. The preparation method according to claim 1, characterized in that, The green long afterglow luminescent material MgAl2O4:Ce 3+ And red long afterglow luminescent material CaTiO3:Pr 3+ The mass ratio is 0.5~1:

1.

5. The preparation method according to claim 1, characterized in that, The leuco dye microcapsule thermochromic material turns green upon temperature change.

6. The preparation method according to claim 4 or 5, characterized in that, The mass ratio of the temperature-responsive color-changing pigment to the rare earth long-afterglow luminescent material is 0.04~0.1:1; the mass ratio of the total mass of the temperature-responsive color-changing pigment and the rare earth long-afterglow luminescent material to the mass of the PAN primary spinning solution is 0.02~0.06:

1.

7. The preparation method according to claim 1, characterized in that, The defoaming treatment is performed at a pressure of 300-600 Torr for 5-10 minutes.

8. The preparation method according to claim 1, characterized in that, The conditions for wet spinning include: a feed rate of 4-8 mm / min; a spinneret diameter of 0.15-0.55 mm; a coagulation bath consisting of a mixture of organic solvent and water, with a mass concentration of 10-30% for the organic solvent and a coagulation bath temperature of 20-50°C; during the wet spinning process, the spinneret is first stretched 1.5-3 times in the coagulation bath, and then stretched 2-4 times in the water bath at a temperature of 80-100°C.

9. Temperature-responsive dynamic light-emitting fibers prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the temperature-responsive dynamic light-emitting fiber as described in claim 9 in the field of automotive ambient interior design.

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