Modified luminescent material, method for producing the same, luminescent fiber composition, luminescent fiber material, and methods for producing the same

Abstract

The application relates to the technical field of material preparation, and discloses a modified luminescent material, wherein the material comprises: 10-450 parts by weight of a luminescent material and 5-50 parts by weight of a coupling agent; wherein the luminescent material and the coupling agent contain the same metal element; the coupling agent in the modified luminescent material and the luminescent material contain the same element, the similarity of the structures and functional groups of the two is given, the compatibility between the two is good, hydrolysis is not prone to occur, the stability of the modified luminescent material is improved, and a luminescent fiber material prepared from the aforementioned modified luminescent material has excellent mechanical properties and optical properties, and is also high in stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of material preparation, in particular to a modified luminescent material, a preparation method thereof, a luminescent fiber composition, a luminescent fiber material and a preparation method thereof. BACKGROUND

[0002] Ultra-high molecular weight polyethylene (UHMWPE) fiber, also known as high-strength and high-modulus polyethylene fiber, is one of the three high-tech fibers in the world together with carbon fiber and aramid fiber. UHMWPE fiber is a fiber made of polyethylene with a molecular weight of more than 1 million by spinning and super-drawing, which has high strength, high modulus, low density, impact resistance, wear resistance and low elongation at break, and is widely used in bulletproof protection, ocean engineering, transportation, sports equipment, biomedical and home textile products, etc. It has a large demand in military and civilian fields.

[0003] With the development of science and technology, single-property fiber raw materials have been unable to meet the increasing demand for functional textiles. In the field of ultra-high molecular weight polyethylene fiber, although its application prospect is broad, numerous fiber materials based on UHMWPE have been developed, but high-strength and high-modulus UHMWPE fiber with luminescent properties still has deficiencies.

[0004] CN114808188A discloses a blue-green double-color self-luminescent fiber and a preparation method thereof, which comprises a skin layer and a core layer. The skin layer comprises polyamide and rare earth strontium magnesium silicate long-afterglow luminescent material, and the core layer comprises polyester and rare earth strontium aluminate luminescent material. However, it has not been industrialized and applied, and the fiber matrix is limited to polyamide and polyester, which is not suitable for polyethylene or polypropylene. In addition, the bonding force and stability between the core layer and the skin layer are poor, which is not conducive to the preparation of high-strength and high-modulus luminescent fiber.

[0005] CN111962180A discloses a red long-afterglow luminescent composite fiber filament and a preparation method thereof. The red long-afterglow luminescent composite fiber filament comprises a skin layer and a core layer. The core layer comprises polyester and SrAl2O4:Eu 2+ ,Dy 3+ luminescent material, and the skin layer comprises polyamide 6 and a red fluorescent color converter. However, it has not been industrialized and applied, and the rare earth aluminate luminescent material is easily affected by moisture in the air, which is unstable in properties and limits its service life.

[0006] CN110318109A discloses a rare earth luminescent fiber, which aims to provide a rare earth luminescent fiber with high temperature resistance, anti-denaturation and strong practicability. The present application is suitable for the technical field of textile materials, but it has not been industrialized and applied. Moreover, the cellulose fiber used has high production cost, is prone to moisture, has poor toughness and poor corrosion resistance, which is not conducive to the mechanical properties and dimensional stability of the product.

[0007] CN109913972A discloses a luminescent composite fiber and a preparation method thereof. The preparation method is simple, the amount of silk fibroin and long afterglow rare earth can be selected according to different afterglow function requirements, and the silk fibroin and long afterglow rare earth do not cause any damage to the structure and performance of the blended fiber. However, the silk fibroin has low strength and modulus, is easy to hydrolyze, and has poor resistance to acids and bases, which limits its application field.

[0008] Therefore, it is necessary to develop a UHMWPE fiber with good stability and luminescent properties. SUMMARY

[0009] The present application aims to overcome the problems of poor stability of luminescent materials and lack of industrialization in the prior art, and provides a modified luminescent material, a preparation method thereof, a luminescent fiber composition, and a luminescent fiber material and a preparation method thereof.

[0010] To achieve the above-mentioned purpose, the first aspect of the present application provides a modified luminescent material, wherein the material comprises: 10-450 parts by weight of a luminescent material and 5-50 parts by weight of a coupling agent; wherein the luminescent material and the coupling agent contain the same metal element.

[0011] The second aspect of the present application provides a preparation method of a modified luminescent material, wherein at a first temperature, a luminescent material is dissolved in a first solvent to obtain a first solution, and at a second temperature, a coupling agent is dissolved in a second solvent to obtain a second solution; the first solution and the second solution are mixed and dried to obtain the modified luminescent material; wherein the luminescent material is 10-450 parts by weight and the coupling agent is 5-50 parts by weight, and the luminescent material and the coupling agent contain the same metal element.

[0012] The third aspect of the present application provides a composition for preparing a luminescent fiber, wherein the composition comprises: ultrahigh molecular weight polyethylene, a modified luminescent material, a spinning aid and a solvent; wherein the modified luminescent material is the modified luminescent material or the modified luminescent material prepared by the aforementioned method.

[0013] The fourth aspect of the present application provides a luminescent fiber material, wherein the luminescent fiber has a fineness of 2-200 dtex, a breaking strength of 10-50 cN / dtex, an initial modulus of 500-1700 cN / dtex, a breaking elongation of 1-5%, an elongation coefficient of variation of 1-7 CV%, a strength coefficient of variation of 1-5 CV%, an initial brightness of 0.5-6 cd / m 2 , and an afterglow time of 0.5-6 h; the luminescent fiber is prepared by spinning the aforementioned composition.

[0014] The fifth aspect of the present application provides a preparation method of a luminescent fiber material, wherein, in a solvent, ultrahigh molecular weight polyethylene, modified luminescent material and spinning aid are mixed uniformly for swelling, the mixed and uniformly swelled solution is extruded to obtain a gel filament, and the gel filament is subjected to quenching, drying, drawing and winding to obtain the luminescent fiber.

[0015] Through the above technical solution, the present application has the following excellent effects:

[0016] (1) The coupling agent and the luminescent material have the same metal element, which gives the similarity of the structure and functional groups of the two, and good compatibility between each other, so that the coupling agent and the luminescent material are mixed more fully, the stability of the modified luminescent material is improved, and hydrolysis is not easy to occur; further, the optical performance, mechanical performance and stability of the prepared luminescent fiber material are improved;

[0017] (2) In the preparation process of the luminescent fiber material, through the step of step-by-step preparation, the modified luminescent material is uniformly dispersed in the ultrahigh molecular weight polyethylene, and the solvents of each module can be recycled, which is conducive to industrialization promotion;

[0018] (3) The synergistic effect of each component in the composition of the luminescent fiber makes the filler more uniformly dispersed in the ultrahigh molecular weight polyethylene, reduces the agglomeration behavior of each component in the composition in the ultrahigh molecular weight polyethylene, and improves the stability of the prepared luminescent fiber; and the addition of the modified luminescent material with a specific proportion and components in the luminescent fiber improves the photon utilization efficiency and luminescence quantum yield on the basis of maintaining good mechanical properties, so that it has higher initial brightness and longer afterglow time, gives the luminescent fiber material excellent optical performance, mechanical performance and stability, and enables the luminescent fiber to be applied within a certain humidity range, not easy to hydrolyze and have a long service life. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is a microscope image of the luminescent fiber prepared in Example 4 of the present application;

[0020] Figure 2 is a structural schematic diagram of the luminescent fiber of the present application;

[0021] Figure 3 is a schematic diagram of the fiber spinning equipment process of the present application;

[0022] Figure 4 is a schematic diagram of the fiber spinning process of the present application. DETAILED DESCRIPTION

[0023] The specific embodiments of the present application are described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and explanatory and are not intended to limit the present application.

[0024] The first aspect of the present application provides a modified luminescent material, wherein the material comprises 10-450 parts by weight of a luminescent material and 5-50 parts by weight of a coupling agent; wherein the luminescent material and the coupling agent comprise the same metal element.

[0025] The inventors have unexpectedly found that when the luminescent material and the coupling agent comprise the same metal element, the functional groups and structures of the luminescent material and the coupling agent have commonalities, good compatibility with each other, are not prone to hydrolysis, and are more likely to form a uniform and stable material, thereby improving the utilization efficiency of photons and the luminescent quantum yield, and enabling the modified luminescent material to have excellent luminescent performance.

[0026] Further, the material comprises 30-240 parts by weight of a luminescent material and 10-30 parts by weight of a coupling agent; wherein the metal element is Ti.

[0027] According to the present application, the mass ratio of the luminescent material to the coupling agent is 2-9:1, preferably 3-8:1.

[0028] In the present application, when the weight ratio of the luminescent material to the coupling agent is 3.5:1, the modified luminescent material has the best luminescent performance. When the content of the coupling agent is too high, the decrease in quenching effect is not sufficient to compensate for the decrease in excitation quantum efficiency, resulting in a decrease in optical performance.

[0029] According to the present application, the luminescent material is selected from at least one of the following: titanium salts, preferably Ca2Zn4Ti5O 36 :Pr 3+ , Mg 0.2 Ca 0.8 TiO3:Pr 3+ , and CaTiO3:Pr 3+ .

[0030] According to the present application, the coupling agent is selected from titanium ester coupling agents.

[0031] In the present application, the specific coupling agent has the advantage of wide application range for fillers, coupling agents, and resins compared to the coupling agents on the market. Specifically, the titanium ester coupling agent is suitable for fillers, coupling agents, and resins, and has a wide application range, while the widely used silane coupling agent on the market is mainly suitable for thermosetting resins. Silane coupling agents are only effective for fillers containing silicon elements, while titanium ester coupling agents are suitable for a variety of fillers, and also have a wide range of suitable resins; at the same time, they can play a synergistic role with titanium salts, enhance the mechanical properties of fibers, and help improve the luminescent performance.

[0032] Further, the luminescent material is Ca2Zn4Ti5O 36 :Pr 3+ .

[0033] Further, the coupling agent is selected from at least one of a monoalkoxy titanate coupling agent, a chelate-type titanate coupling agent and a coordination-type titanate coupling agent, more preferably a monoalkoxy pyrophosphonate-type titanate coupling agent and / or a monoalkoxy fatty acid ester-type titanate coupling agent, most preferably a monoalkoxy pyrophosphonate-type titanate coupling agent.

[0034] The second aspect of the present application provides a preparation method of a modified luminescent material, wherein, at a first temperature, a luminescent material is dissolved in a first solvent to obtain a first solution, at a second temperature, a coupling agent is dissolved in a second solvent to obtain a second solution; the first solution and the second solution are mixed and dried to obtain the modified luminescent material; wherein the luminescent material is 10-450 parts by weight and the coupling agent is 5-50 parts by weight, and the luminescent material and the coupling agent contain the same metal element.

[0035] According to the present application, the luminescent material is 30-240 parts by weight and the coupling agent is 10-30 parts by weight; and the metal element is Ti.

[0036] According to the present application, the mass ratio of the luminescent material to the coupling agent is 2-9:1, preferably 3-8:1.

[0037] According to the present application, the luminescent material is ultrasonically dissolved in the first solvent for 0.5-6h, and the coupling agent is ultrasonically dissolved in the second solvent for 1-5h.

[0038] In the present application, the luminescent material and the coupling agent are respectively dissolved in the first solvent and the second solvent at different temperatures, and the dissolution is made more sufficient by using ultrasonic, which brings deep infiltration and mixing at the molecular level, and does not depend on high-temperature stirring, effectively avoiding the damage to the structural stability of the substrate caused by high temperature.

[0039] In the present application, ultrasonic can accelerate the dissolution, mixing and reaction of compounds and solvents at the molecular level under mild conditions (such as room temperature, without mechanical stirring), improve the reaction efficiency and blending effect, and help to realize energy saving, environmental protection and cost reduction and efficiency increase of the process.

[0040] According to the present application, the luminescent material is ultrasonically dissolved in the first solvent for 2-4h, and the coupling agent is ultrasonically dissolved in the second solvent for 2-3h.

[0041] According to the present application, the first temperature is 10-120℃.

[0042] According to the present application, the second temperature is 10-35℃.

[0043] In the present application, the first temperature and the second temperature meeting the above range can enhance the compatibility between the luminescent material and the coupling agent, so that the modified luminescent material prepared finally has improved stability and good luminescent performance.

[0044] Further, the first temperature is 20-100℃.

[0045] Further, the second temperature is 20-30℃.

[0046] According to the present application, the weight ratio of the luminescent material to the first solvent is 0.05-0.2:1.

[0047] According to the present application, the weight ratio of the coupling agent to the second solvent is 0.01-0.25:1.

[0048] In the present application, when the reactants meeting the above range weight ratio are reacted, they have good compatibility with each other and are not prone to hydrolysis, the modified luminescent material prepared finally is uniform and stable, and has excellent luminescent performance.

[0049] Further, the weight ratio of the luminescent material to the first solvent is 0.1-0.15:1.

[0050] Further, the weight ratio of the coupling agent to the second solvent is 0.05-0.15:1.

[0051] According to the present application, the first solvent and the second solvent are each independently selected from at least one of decalin, chloroform, and tetrahydrofuran, preferably decalin and / or chloroform.

[0052] In the present application, the first solvent and the second solvent in the preparation method of the modified luminescent material are both low-boiling-point solvents, which can be recycled, and the recycled solvents can be reused in the dry spinning module, thereby reducing the cost and being environmentally friendly.

[0053] In the present application, the luminescent material and the coupling agent in the second aspect are each described above and will not be repeated.

[0054] The third aspect of the present application provides a composition for preparing a luminescent fiber, wherein the composition comprises: ultrahigh molecular weight polyethylene, a modified luminescent material, a spinning aid, and a solvent; wherein the modified luminescent material is the aforementioned modified luminescent material or the modified luminescent material prepared by the aforementioned method.

[0055] According to the present application, the amount of the ultrahigh molecular weight polyethylene is 5wt%-20wt%, preferably 7wt%-15wt%, based on the amount of the solvent.

[0056] According to the application, the amount of the modified luminescent material is 2wt%-20wt% and the amount of the spinning aid is 0.1wt%-1.5wt% based on the amount of the ultra-high molecular weight polyethylene.

[0057] In the application, the specific amount of each component in the composition can make the fiber prepared by spinning of the composition have good mechanical properties and optical properties at the same time; when the modified luminescent material is less than this amount, the physical crosslinking points are insufficient, and the mechanical properties of the fiber are poor; when the modified luminescent material is more than this amount, the optical properties have been saturated and will not increase any more, but with the increase of the amount, the crystallinity and integrity of the chain segment of the fiber will be affected, and the mechanical properties will decrease.

[0058] Preferably, the amount of the modified luminescent material is 2wt%-10wt% and the amount of the spinning aid is 0.6wt%-1.5wt% based on the amount of the ultra-high molecular weight polyethylene.

[0059] Further, the inventor of the application finds that when the amount of the modified luminescent material is 9wt%, the luminescent fiber has the best mechanical properties and optical properties at the same time.

[0060] According to the application, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 1 million-20 million g / mol, preferably 2 million-6 million g / mol.

[0061] According to the application, the spinning aid includes an antistatic agent, an antioxidant and a lubricant.

[0062] In the application, the spinning aid of the specific component can improve the forming processability and processing stability of the fiber, solve the surface migration problem of the material, reduce the melt viscosity, shorten the plasticizing time, increase the unit output, and enhance the stability, creep resistance, oxidation resistance and aging resistance of the luminescent fiber product.

[0063] According to the application, the antistatic agent is selected from at least one of derivatives of sulfuric acid ester, phosphoric acid ester and polyethylene glycol, preferably at least one of alkyl phosphate, alkyl sulfonate and polyoxyethylene alkyl phosphate ester salt.

[0064] According to the application, the antioxidant is selected from at least one of antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant 1178 and 2,6-di-tert-butyl-p-cresol, preferably antioxidant 168 and / or 2,6-di-tert-butyl-p-cresol.

[0065] According to the application, the lubricant is selected from at least one of stearic acid, butyl stearate, oleamide, ethylene bis-stearamide, polyethylene wax and low molecular weight polypropylene, preferably stearic acid and / or butyl stearate.

[0066] According to the application, the content of the antistatic agent is 0.02wt%-0.4wt%, the content of the antioxidant is 0.04wt%-0.6wt%, and the content of the lubricant is 0.02wt%-0.5wt%, based on the amount of the ultra-high molecular weight polyethylene.

[0067] In the application, the specific content of the spinning aid has the modification effect and good compatibility and internal plasticity of the fiber resin matrix, solves the surface migration problem of the plasticizer, can improve the forming processability and processing stability of the fiber, reduce the melt viscosity, shorten the plasticizing time, increase the unit output, and enhance the stability, creep resistance, oxidation resistance and aging resistance of the luminous fiber product.

[0068] Further, the content of the antistatic agent is 0.05wt%-0.2wt%, the content of the antioxidant is 0.1wt%-0.3wt%, and the content of the lubricant is 0.08wt%-0.3wt%, based on the amount of the ultra-high molecular weight polyethylene.

[0069] According to the application, the solvent is selected from at least one of benzene, 1,2,3,4-tetrahydronaphthalene, decalin and xylene, preferably decalin and / or 1,2,3,4-tetrahydronaphthalene.

[0070] The fourth aspect of the application provides a luminous fiber material, wherein the fiber fineness of the luminous fiber is 2-200dtex, the breaking strength is 10-50cN / dtex, the initial modulus is 500-1700cN / dtex, the elongation at break is 1-5%, the elongation coefficient of variation is 1-7CV%, the strength coefficient of variation is 1-5CV%, the initial brightness is 0.5-6cd / m 2 , and the afterglow time is 0.5-6h; the luminous fiber is prepared by spinning the aforementioned composition.

[0071] In the application, the stability of the fiber is characterized by the elongation coefficient of variation and the strength coefficient of variation. The initial brightness of the luminous fiber material of the application is strong, the afterglow time is long, the mechanical properties are good, and the stability is high.

[0072] Figure 2 It is a structural schematic diagram of the luminous fiber of the application. The modified luminous material is uniformly distributed in the ultra-high molecular weight polyethylene matrix, which can reduce the variation rate of the mechanical properties and realize uniform distribution of the luminous area, greatly improve the mechanical and optical properties of the fiber product, and improve the uniformity of the product quality, thereby meeting the needs of the actual application field.

[0073] The fifth aspect of the present application provides a preparation method of a luminescent fiber material, wherein, in a solvent, ultrahigh molecular weight polyethylene, modified luminescent material and spinning auxiliary agent are mixed uniformly for swelling, the mixed and uniformly swelled solution is extruded to obtain a gel filament, and the gel filament is subjected to quenching, drying, drawing and winding to obtain the luminescent fiber.

[0074] According to the present application, the quenching solvent is at least one of toluene, 1,2,3,4-tetrahydronaphthalene, decalin, xylene, water and ethanol; preferably water and / or ethanol.

[0075] In the present application, the spinning method is a common dry spinning method in the art, and the specific equipment is as shown in Figure 3 The process flow of the present application is short as shown in Figure 4 The solvent of the dry spinning method coincides with the solvent used in the preparation of the modified luminescent material in the previous step, and the solvent can be recycled, continuous production can be realized, the production cost is reduced, and the environmental protection is facilitated.

[0076] According to the present application, the swelling temperature is 70-120℃, preferably 90-110℃; and the swelling time is 1-8h, preferably 2-5h.

[0077] According to the present application, the extrusion rate is 0-40m / min, preferably 15-30m / min.

[0078] According to the present application, the quenching temperature is -50℃ to 20℃, preferably -15℃ to -5℃; and the quenching time is 0.2-5min, preferably 0.5-2min.

[0079] According to the present application, the drying is carried out in a drying hot box, and the drying method is blowing, and the air direction is opposite to the running direction of the gel filament.

[0080] According to the present application, the blowing gas is independently selected from at least one of air, nitrogen, carbon dioxide and inert gas; preferably at least one of air, nitrogen, carbon dioxide, argon and helium.

[0081] According to the present application, the pre-drawing is carried out in a drawing hot box.

[0082] According to the present application, the pre-drawing multiple is 1-10 times, preferably 1-5 times; and the pre-drawing temperature is 100-150℃, preferably 110-130℃.

[0083] According to the present application, the multi-stage drawing includes primary drawing, secondary drawing and tertiary drawing, the primary drawing multiple is 4-6 times, preferably 4.5-5.5 times; and the primary drawing temperature is 100-140℃, preferably 125-140℃.

[0084] According to the present application, the multiple of the secondary drawing is 1-3 times, preferably 1.5-2.5 times; the temperature of the secondary drawing is 130-150°C, preferably 135-145°C.

[0085] According to the present application, the multiple of the tertiary drawing is 1-2 times, preferably 1.2-1.5 times; the temperature of the tertiary drawing is 140-160°C, preferably 145-155°C.

[0086] The present application will be described in detail by way of examples.

[0087] The detection method of breaking strength: using Instron 1122 universal material testing machine: the fibers prepared under different conditions are stretched, and the environmental control is carried out according to the requirements of the standard test method for reinforcing materials, the temperature is 23±2°C, and the relative humidity is (50±10)%. The stretching speed is 250mm / min; the clamp is the rope test clamp produced by INSTRON company, which can ensure that the sample does not slip during the test; the clamping distance is 500mm. Stretching until the fiber is broken, and the instrument automatically gives the result. The average test is carried out for 10 times per barrel, and the average value is taken, and the breaking strength result is given by the software;

[0088] The detection method of breaking elongation is the same as above, and the result is given by the software;

[0089] The detection method of initial modulus is the same as above, and the result is given by the software;

[0090] The detection method of elongation coefficient of variation is the same as above, and the result is given by the software;

[0091] The detection method of strength coefficient of variation is the same as above, and the result is given by the software;

[0092] The microscope is selected as Cai Kang optical CKC2000 high-definition digital imaging microscope.

[0093] The detection method of initial brightness is: using PR-305 type long afterglow fluorescence tester. When testing, select the standard light source with excitation light intensity of 1000lx to continuously excite for 10 minutes, and record the initial brightness of afterglow after excitation;

[0094] The detection method of afterglow time is: using PR-305 type long afterglow fluorescence tester. When testing, select the standard light source with excitation light intensity of 1000lx to continuously excite for 10 minutes, and record the afterglow brightness decay to 0.00032cd / m 2 The required time is the afterglow time of the material.

[0095] Luminescent material: Ca2Zn4Ti5O 36 :Pr 3+ , Mg0.2 Ca 0.8 TiO3:Pr 3+ CaTiO3:Pr 3+ SrAl2O4:Eu 2+ Dy 3+ Sr3MgSi2O8:Eu 2+ Dy 3+ ZnWO4:Eu 3+ and Zn3(PO4):Mn 2+ Purchased from Aladdin Reagents Company;

[0096] KH550, monoalkoxypyrophosphate type titanate coupling agent, monoalkoxy fatty acid ester type titanate coupling agent, chelating titanate coupling agent, coordination titanate coupling agent, etc. were purchased from Anaiji Reagent Company.

[0097] Ultra-high molecular weight polyethylene A1 (viscosity-average molecular weight of 4 million g / mol) was purchased from Lianle Chemical.

[0098] Ultra-high molecular weight polyethylene A2 (viscosity-average molecular weight of 500,000 g / mol) was purchased from Yanshan Petrochemical.

[0099] Antistatic agents such as alkyl sulfates, phosphates, polyethylene glycol derivatives, alkyl phosphates, alkyl sulfonates, polyoxyethylene alkyl phosphates, and polyoxyethylene alkyl phosphate salts were purchased from Bid Reagent Company.

[0100] Antioxidant 1076, Antioxidant 1010, Antioxidant 168, Antioxidant 1178, and 2,6-di-tert-butyl-p-cresol were purchased from Aladdin Reagent Company.

[0101] Lubricants such as stearic acid, butyl stearate, oleamide, ethylene bis-stearamide, polyethylene wax and low molecular weight polypropylene were purchased from Mairui Reagent Company.

[0102] Decahydronaphthalene, chloroform, and methanol were purchased from Sinopharm Reagent Chemical Company.

[0103] Preparation Example 1

[0104] At 25℃, 40g of Ca2Zn4Ti5O 36 :Pr 3+ Add 400g of decahydronaphthalene and sonicate for 2h to obtain the first solution; at 25°C, add 10g of monoalkoxypyrophosphate titanate coupling agent to 180g of decahydronaphthalene and sonicate for 3h to obtain the second solution; mix the first solution and the second solution and dry to obtain the modified luminescent material preparation example 1.

[0105] Preparation Examples 2-12 and Comparative Examples 1-6 were carried out according to the method of Preparation Example 1, and the specific additions are shown in Table 1.

[0106] Table 1

[0107]

[0108] Table 1 (continued)

[0109]

[0110]

[0111] Table 1 (continued)

[0112]

[0113] Table 1 (continued)

[0114]

[0115] Table 1 (continued)

[0116]

[0117]

[0118] Table 1 (continued)

[0119]

[0120] Example 1

[0121] 5000 g of UHMWPE Al was added to 45000 g of decalin, and then 450 g of the product of Preparation Example 1, 7.5 g of an antistatic agent, 10 g of an antioxidant, and 12.5 g of a lubricant were added and mixed to swell. The swelling temperature was 100°C, and the swelling time was 4 h. The extrusion rate was 2 m / min. The quenching temperature was -10°C, and the quenching time was 1 min. The drying oven temperature was 60°C. The pre-drawing multiple was 2, the drawing oven temperature was 110°C. The first drawing multiple was 5, and the first drawing temperature was 138°C. The second drawing multiple was 1.5, and the second drawing temperature was 144°C. The third drawing multiple was 1.2, and the third drawing temperature was 148°C.

[0122] Examples 2-12, 14-25 and Comparative Examples 1-7 were prepared according to the method of Example 1. The specific components added are shown in Table 2.

[0123] Table 2 Table 2 (continued)

[0124]

[0125]

[0126] Table 2 (continued)

[0127]

[0128] Table 2 (continued)

[0129]

[0130]

[0131] Table 2 (continued)

[0132]

[0133] Table 2 (continued)

[0134]

[0135] Table 2 (continued)

[0136] Table 2 (continued)

[0137]

[0138] Example 13

[0139] Example 13 5000 g of UHMWPE Al was added to 45000 g of decalin, and then 450 g of the product of Preparation 2, 7.5 g of antistatic agent, 10 g of antioxidant and 12.5 g of lubricant were added and mixed to swell. The swelling temperature was 100°C, the swelling time was 4 h, the extrusion rate was 3 m / min; the quenching temperature was 0°C, the quenching time was 1 min; the drying oven temperature was 60°C; the pre-drawing multiple was 2, the drawing oven temperature was 110°C; the first drawing multiple was 4.6, the first drawing temperature was 136°C; the second drawing multiple was 1.5, the second drawing temperature was 145°C; the third drawing multiple was 1.2, and the third drawing temperature was 150°C.

[0140] The mechanical parameters of the fibers prepared in Examples 1-25 and Comparative Examples 1-7 are shown in Table 3.

[0141] Table 3

[0142]

[0143]

[0144] The optical parameters of the fibers prepared in Examples 1-25 and Comparative Examples 1-7 are shown in Table 4.

[0145] Table 4

[0146]

[0147]

[0148] From the results of Table 3 and Table 4, it can be seen that the type of luminescent material has an impact on the performance of the luminescent fiber compared to Examples 1-12, when the luminescent material in the modified luminescent material and the coupling agent contain the same elements, the finally prepared luminescent fiber can have mechanical properties and optical properties, and has stronger stability, wherein the luminescent material is Ca2Zn4Ti5O 36 :Pr 3 + , Mg 0.2 Ca 0.8 TiO3:Pr 3+ and CaTiO3:Pr 3+ have good effects, when the luminescent material is Ca2Zn4Ti5O 36 :Pr 3+ , the performance is more excellent;

[0149] Further, Examples 2-7 adjust the amount of luminescent material and coupling agent, the functional groups and structures of the luminescent material and the coupling agent have commonality, and have good compatibility with each other, are not prone to hydrolysis, and are more likely to form a uniform and stable material, while improving the photon utilization efficiency and luminescence quantum yield; when the content of the coupling agent is too high, the decrease in the quenching effect is not enough to make up for the decrease in the excitation quantum efficiency, resulting in a decrease in optical performance, so the specific amount of luminescent material and coupling agent makes the photon utilization efficiency and luminescence quantum yield of the modified luminescent material higher, and has excellent luminescent performance;

[0150] From the microscope image of the luminescent fiber prepared in Example 4 (see Figure 1 ), it can be seen that the prepared long afterglow luminescent ultrahigh molecular weight polyethylene fiber has similar diameter, size uniformity and smooth surface, the products (a) and (b) of different batches under the same conditions have similar morphology and structure, and the repeatability of fiber spinning preparation can be realized, and the prepared fiber has good surface morphology index, size stability and spinnability;

[0151] Examples 14-21 adjust the amount of modified luminescent material and ultrahigh molecular weight polyethylene, based on the amount of ultrahigh molecular weight polyethylene, the modified luminescent material is preferably 2wt%-20wt%, more preferably 2wt%-10wt; too little modified luminescent material will affect the luminescent intensity, and too much modified luminescent material will not be conducive to improving the luminescence quantum yield and improving the fiber crystallinity, which will affect the luminescent performance and mechanical properties;

[0152] In the spin-facilitating agent of Embodiment 22 and Embodiment 23, preferably, the content of the antistatic agent is 0.05wt%-0.2wt%, preferably alkyl phosphate, the content of the antioxidant is 0.1wt%-0.3wt%, preferably antioxidant 168, and the content of the lubricant is 0.08wt%-0.3wt%, preferably polyethylene wax; the spin-facilitating agent with specific components can improve the forming processability and processing stability of the fiber, solve the surface migration problem of the material, and reduce the melt viscosity, shorten the plasticizing time, and at the same time, increase the unit output, and the prepared luminous fiber material has excellent stability, creep resistance, oxidation resistance and aging resistance;

[0153] In Embodiment 24 and Embodiment 25, the concentration and molecular weight of the ultrahigh molecular weight polyethylene are adjusted; when the polymer concentration is 7wt%-15wt% and the molecular weight is 4 million g / mol, it is more beneficial to prepare the luminous fiber material. If the polymer concentration is too high, the viscosity during preparation will be too high, which will make the processing and drawing difficult, and affect the final performance of the product; if the molecular weight of the polymer is too low, it will have a negative impact on the mechanical properties of the finally prepared luminous fiber material; if the molecular weight is too high, it will cause processing difficulties, affect the subsequent spinning and drawing, and thus affect the mechanical properties;

[0154] In Comparative Examples 1-7, the luminous system and coupling agent outside the preferred range are adjusted, which proves that the coupling agent and the luminous material in the embodiment have the same metal element, and the similarity of the structure and functional groups between them has excellent compatibility, so that the coupling agent and the luminous material are more fully mixed, thereby improving the stability and hydrolysis stability of the modified luminous material, and the luminous fiber prepared from the modified luminous material has excellent mechanical properties and optical properties, and the stability is also greatly improved.

[0155] At the same time, the low-boiling-point solvent in the specific implementation can be recycled and used in each module, which reduces the cost and is conducive to industrialization.

[0156] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A modified luminescent material, characterized by, The material comprises: a luminescent material 10-450 parts by weight and a coupling agent 5-50 parts by weight; The luminescent material and the coupling agent comprise the same metal element; The metal element is Ti; The luminescent material is at least one of Ca2Zn4Ti5O 36 :Pr 3+ , Mg 0.2 Ca 0.8 TiO3:Pr 3+ and CaTiO3:Pr 3+ ​ The coupling agent is selected from a titanate coupling agent.

2. The modified luminescent material of claim 1, wherein, The material comprises: the luminescent material 30-240 parts by weight and the coupling agent 10-30 parts by weight; And / or, the mass ratio of the luminescent material to the coupling agent is 2-9:

1.

3. The modified luminescent material of claim 2, wherein, The mass ratio of the luminescent material to the coupling agent is 3-8:

1.

4. The modified luminescent material according to claims 1 to 3, characterized in that The luminescent material is Ca2Zn4Ti5O 36 :Pr 3 + ; And / or, the coupling agent is at least one of a monoalkoxy titanate coupling agent, a chelate type titanate coupling agent and a coordination type titanate coupling agent. The coupling agent is a monoalkoxy pyrophosphonate type titanate coupling agent and / or a monoalkoxy fatty acid ester type titanate coupling agent.

5. The modified luminescent material of claim 4, wherein, The coupling agent is a monoalkoxy pyrophosphonate type titanate coupling agent.

6. The modified luminescent material of claim 5, wherein, At a first temperature, the luminescent material is dissolved in a first solvent to obtain a first solution, and at a second temperature, the coupling agent is dissolved in a second solvent to obtain a second solution; the first solution and the second solution are mixed and dried to obtain the modified luminescent material; wherein the luminescent material is 10-450 parts by weight and the coupling agent is 5-50 parts by weight, and the luminescent material and the coupling agent comprise the same metal element.

7. A method for producing the modified luminescent material according to any one of claims 1 to 6, characterized by, The luminescent material 30-240 parts by weight and the coupling agent 10-30 parts by weight; the metal element is Ti; 8. The preparation method according to claim 7, characterized in that, And / or, the mass ratio of the luminescent material to the coupling agent is 2-9:1; And / or, the luminescent material is dissolved in a first solvent for 0.5-6h under ultrasonic; the coupling agent is dissolved in a second solvent for 1-5h under ultrasonic; And / or, the first temperature is 10-120℃; And / or, the second temperature is 10-35℃; And / or, the weight ratio of the luminescent material to the first solvent is 0.05-0.2:1; And / or, the weight ratio of the coupling agent to the second solvent is 0.01-0.25:1; And / or, the first solvent and the second solvent are each independently selected from at least one of decalin, chloroform and tetrahydrofuran. The mass ratio of the luminescent material to the coupling agent is 3-8:

1.

9. The production method according to claim 8, characterized by, And / or, the luminescent material is dissolved in a first solvent for 2-4h under ultrasonic; the coupling agent is dissolved in a second solvent for 2-3h under ultrasonic; And / or, the first temperature is 20-100℃; And / or, the second temperature is 20-30℃; And / or, the weight ratio of the luminescent material to the first solvent is 0.1-0.15:1; And / or, the weight ratio of the coupling agent to the second solvent is 0.05-0.15:1; And / or, the first solvent and the second solvent are each independently selected from decalin and / or chloroform. The composition comprises: ultra-high molecular weight polyethylene, modified luminescent material, spinning aid and solvent; 10. A composition for making a luminescent fiber, characterized in that, The modified luminescent material is the modified luminescent material of any one of claims 1-6, or the modified luminescent material prepared by the preparation method of any one of claims 7-9; The spinning aid comprises antistatic agent, antioxidant and lubricant. ​ 11. The composition of claim 10, wherein, The amount of the ultra-high molecular weight polyethylene is 5wt%-20wt% based on the amount of the solvent; and / or, the amount of the modified luminescent material is 2wt%-20wt% and the amount of the spinning aid is 0.1wt%-1.5wt% based on the amount of the ultra-high molecular weight polyethylene.

12. The composition of claim 11, wherein, The amount of the ultra-high molecular weight polyethylene is 7wt%-15wt% based on the amount of the solvent; and / or, the amount of the modified luminescent material is 2wt%-10wt% and the amount of the spinning aid is 0.6wt%-1.5wt% based on the amount of the ultra-high molecular weight polyethylene.

13. The composition according to any one of claims 10 to 12, characterized in that, The viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 100 million-2000 million g / mol; and / or, the antistatic agent is selected from at least one of derivatives of sulfuric acid ester, phosphoric acid ester and polyethylene glycol; and / or, the antioxidant is selected from at least one of antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant 1178 and 2,6-di-tert-butyl-p-cresol; and / or, the lubricant is selected from at least one of stearic acid, butyl stearate, oleamide, ethylene bis-stearamide, polyethylene wax and low molecular weight polypropylene; and / or, the content of the antistatic agent is 0.02wt%-0.4wt%, the content of the antioxidant is 0.04wt%-0.6wt% and the content of the lubricant is 0.02wt%-0.5wt% based on the amount of the ultra-high molecular weight polyethylene; and / or, the solvent is selected from at least one of benzene, 1,2,3,4-tetrahydronaphthalene, decalin and xylene.

14. The composition of claim 13, wherein, The viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 200 million-600 million g / mol; and / or, the antistatic agent is selected from at least one of alkyl phosphate, alkyl sulfonate and polyoxyethylene alkyl phosphate ester; and / or, the antioxidant is selected from at least one of antioxidant 168 and / or 2,6-di-tert-butyl-p-cresol; and / or, the lubricant is selected from at least one of stearic acid and / or butyl stearate; and / or, the content of the antistatic agent is 0.05wt%-0.2wt%, the content of the antioxidant is 0.1wt%-0.3wt% and the content of the lubricant is 0.08wt%-0.3wt% based on the amount of the ultra-high molecular weight polyethylene; and / or, the solvent is selected from at least one of decalin and / or 1,2,3,4-tetrahydronaphthalene.

15. A light emitting fiber material, characterized by The light emitting fiber has a fineness of 2-200 dtex, a breaking strength of 10-50 cN / dtex, an initial modulus of 500-1700 cN / dtex, a breaking elongation of 1-5%, an elongation coefficient of variation of 1-7 CV%, a strength coefficient of variation of 1-5 CV%, an initial brightness of 0.5-6 cd / m 2 , and a residual light time of 0.5-6 h. The luminescent fiber is prepared by spinning the composition according to any one of claims 10-14.

16. A method of producing the luminescent fiber material according to claim 15, characterized in that The ultra-high molecular weight polyethylene, the modified luminescent material and the spinning aid are mixed uniformly in a solvent to swell, the mixed and swollen solution is extruded to obtain a gel filament, and the gel filament is quenched, dried, drawn and wound to obtain the luminescent fiber.

17. The method of claim 16, wherein, The quenching solvent is at least one of toluene, 1,2,3,4-tetrahydronaphthalene, decalin, xylene, water and ethanol.

18. The method of claim 17, wherein, The quenching solvent is water and / or ethanol.

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