High-brightness photochromic polyester yarn as well as preparation method and application thereof

Abstract

The invention relates to a high-brightness photochromic polyester yarn and a preparation method and application thereof, the high-brightness photochromic polyester yarn comprises a skin layer and a core layer, and the mass ratio of the skin layer to the core layer is 1: (6-8); the skin layer is prepared from the following raw materials: a copolymer prepared from 1, 3-bis (oxirane methyl)-5-(2-allyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, allyltriphenylphosphonium bromide and methyl methacrylate through a free radical copolymerization reaction; the core layer is prepared from the following raw materials: polyester chips, photochromic master batches, W-Mo-Ti-rare earth-B-O, 2, 4-diaminobenzene sulfonic acid, phosphorus pentoxide, polyphosphoric acid, an antistatic agent, and meso-tetramethyl-meso-tetra (p-aminophenyl) calix [4] pyrrole. The antistatic photochromic film is sufficient in antistatic performance, high in breaking strength, good in photochromic stability, high in brightness after color change and good in anti-perspective performance.

Description

Technical Field

[0001] The invention relates to the technical field of photochromic polyester yarns, and in particular to a high-brightness photochromic polyester yarn and a preparation method and application thereof. Background Art

[0002] Polyester yarn refers to yarn spun from polyester. It is widely used in the clothing field because of its advantages such as easy washing and quick drying, acid and alkali resistance, good wear resistance, strong and durable, good elasticity, and not easy to deform. However, polyester yarn itself has no dyeing group, small polarity and volume resistivity of 10 14 -10 15 Ω, which makes the polyester dyeing performance poor and easy to generate static electricity. In the application process, there are defects such as poor color fastness, easy fading, easy to generate static electricity, etc., which makes it difficult to meet people's demand for color beauty. It is in this situation that photochromic polyester yarn came into being, and its appearance has attracted widespread attention in the industry.

[0003] Photochromic polyester yarn has a unique visual effect, which not only meets consumers' pursuit of novelty, diversity and variability in clothing colors, but also can be widely used in anti-counterfeiting, advertising, military camouflage and other fields. However, existing photochromic polyester yarns have more or less technical defects such as insufficient antistatic performance, insufficient breaking strength, insufficient brightness after color change, and the need to further improve the anti-see-through performance.

[0004] In order to solve the above problems, the Chinese invention patent with the authorization announcement number CN118374908B discloses a high-brightness photochromic polyester yarn and its preparation method and application. The yarn includes a skin layer and a core layer, and the mass ratio of the skin layer to the core layer is (3-4): (6-7); the raw materials for preparing the skin layer at least include: modified PET masterbatch and modified MAZO powder; the raw materials for preparing the core layer at least include: photochromic masterbatch and PET slices; the modified PET masterbatch and the modified MAZO powder both contain MAZO powder, and the MAZO powder is prepared by mixing magnesium-doped zinc oxide powder and zinc oxide aluminum powder according to the mass ratio, which overcomes the problem that the skin layer of the existing skin-core structure affects the color effect of the core layer, and at the same time ensures that its mechanical properties can meet the requirements of the subsequent spinning, weaving, dyeing and other processes, and cooperates with the woven fabric structure to ensure the color change effect of the color-changing polyester fabric. However, its antistatic performance and breaking strength still need to be further improved, and the photochromic stability still needs to be further improved.

[0005] It can be seen that the development of a high-brightness photochromic polyester yarn with sufficient antistatic performance, high breaking strength, good photochromic stability, high brightness after color change, and anti-see-through performance, as well as its preparation method and application meet market demand, have broad market value and application prospects, and are of great significance to promoting the development of the field of photochromic polyester yarn. Summary of the invention

[0006] In view of this, the object of the present invention is to provide a high-brightness photochromic polyester yarn with sufficient antistatic performance, high breaking strength, good photochromic stability, high brightness after color change, and anti-see-through performance, as well as a preparation method and application thereof.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] A high-brightness photochromic polyester yarn comprises a skin layer and a core layer, wherein the mass ratio of the skin layer to the core layer is 1:(6-8); the raw materials for preparing the skin layer comprise a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide and methyl methacrylate in a mass ratio of 1:(0.8-1.2):(1-2); the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 5-12 parts of photochromic masterbatch, W-Mo-Ti-rare earth-BO 3-5 parts, 2,4-diaminobenzenesulfonic acid 3-5 parts, phosphorus pentoxide 0.8-1.2 parts, polyphosphoric acid 0.5-0.8 parts, antistatic agent 3-5 parts, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole 1-3 parts.

[0009] Preferably, the preparation method of the meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345.

[0010] Preferably, the antistatic agent is produced by BASF P18 FCA antistatic agent, P16 antistatic agent, At least one of P20 antistatic agents.

[0011] Preferably, the preparation method of W-Mo-Ti-rare earth-BO comprises the following steps: dispersing a tungsten source, a molybdenum source, a titanium source, a rare earth source and a boron source in ethanol, stirring evenly, slowly adding sodium acetate, mixing evenly again to obtain a mixture, transferring the mixture to a polytetrafluoroethylene-lined hydrothermal reactor, and reacting at 195-215°C for 15-22h; cooling to room temperature, repeatedly washing with anhydrous ethanol, drying to constant weight in a vacuum drying oven at 80-90°C, grinding and sieving, and calcining at 600-850°C for 4-6h to obtain W-Mo-Ti-rare earth-BO.

[0012] Preferably, the tungsten source is sodium tungstate; the molybdenum source is molybdenum nitrate; the titanium source is titanium chloride; the rare earth source is at least one of lanthanum nitrate and cerium nitrate; and the boron source is sodium borate.

[0013] Preferably, the mass ratio of the tungsten source, molybdenum source, titanium source, rare earth source, boron source, ethanol and sodium acetate is 1:(0.8-1.2):(0.3-0.5):0.03:0.005:(10-20):3.

[0014] Preferably, the photochromic masterbatch is SunPercept from Suzhou Polydi Material Technology Co., Ltd. TM Ultra series red photochromic masterbatch.

[0015] Preferably, the polyester chips are polyester chips 224 for industrial yarn produced by Sinopec.

[0016] Preferably, the preparation method of the copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide, methyl methacrylate and azobisisobutyronitrile to N,N-dimethylformamide, stirring and reacting for 3-6 hours at 60-70°C in a nitrogen atmosphere, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 85-95°C to constant weight to obtain a copolymer.

[0017] Preferably, the mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, azobisisobutyronitrile and N,N-dimethylformamide is 1:(0.03-0.05):(10-20).

[0018] Another object of the present invention is to provide a method for preparing the high-brightness photochromic polyester yarn, comprising the following steps: first, vacuum-drying the raw materials, mixing the raw materials for the core layer evenly by weight and extruding them through a screw extruder to obtain a core layer material melt, and extruding the copolymer through a screw extruder to obtain a skin layer material melt; the skin layer material melt and the core layer material melt are metered by their own metering pumps and enter a composite spinning box, and then spinning is carried out through a skin-core composite spinning assembly to obtain a high-brightness photochromic polyester yarn.

[0019] Preferably, the spinning temperature is 230-280°C, the cooling air temperature is 15-20°C, the initial spinning speed is 2000-3000m / min, and the stretching multiple is 2-3.

[0020] Another object of the present invention is to provide an application of the high-brightness photochromic polyester yarn in the preparation of photochromic polyester fabrics.

[0021] The beneficial effects of adopting the above technical solution are:

[0022] (1) The high-brightness photochromic polyester yarn provided by the present invention adopts a skin-core composite structure. Through the reasonable selection of skin layer and core layer materials, the compatibility between the two is good, and the stability of the photochromic material in the core layer material is effectively improved; the preparation process is simple, the cost-effectiveness is high, and mass production can be achieved, and it can be applied to the textile field.

[0023] (2) The high-brightness photochromic polyester yarn provided by the present invention comprises a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide and methyl methacrylate in a mass ratio of 1:(0.8-1.2):(1-2); the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 5-12 parts of photochromic masterbatch, 3-5 parts of W-Mo-Ti-rare earth-BO, 3-5 parts of 2,4-diaminobenzenesulfonic acid, 0.8-1.2 parts of phosphorus pentoxide, 0.5-0.8 parts of polyphosphoric acid, 3-5 parts of antistatic agent and 1-3 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole. Through the mutual cooperation and joint action of various raw materials, the polyester yarn products can be given the advantages of sufficient antistatic performance, high breaking strength, good photochromic stability, high brightness after color change, and anti-see-through performance. The amino groups on diaminobenzenesulfonic acid and meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole in the core layer material can react chemically with the epoxy groups introduced by 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione in the skin structure. The sulfonic acid groups on diaminobenzenesulfonic acid can react chemically with the benzene rings on the polyester slices under the catalytic action of phosphorus pentoxide and polyphosphoric acid, so that the skin and core layers can be effectively and firmly combined, thereby improving the performance and structural stability. At the same time, the triazone, triphenylphosphine bromide, ester and p-aminophenyl cup [4] pyrrole structures introduced at the same time, under the multiple effects of electronic effect, steric effect and conjugation effect, make the manufactured product have more sufficient antistatic performance, greater breaking strength, better photochromic stability, higher brightness after color change, and better anti-transmission performance.

[0024] (3) The addition of W-Mo-Ti-rare earth-BO to the high-brightness photochromic polyester yarn provided by the present invention can improve the photochromic effect and also improve the mechanical properties; through the reasonable selection of preparation process parameters, the various performances of the product can be effectively guaranteed to be more excellent, thereby effectively extending its service life. DETAILED DESCRIPTION

[0025] In order to make the technical solution of the present invention better understood by the technical personnel in the field, and to make the above-mentioned features, purposes and advantages of the present invention more clearly understood, the present invention is further described below in conjunction with the embodiments. The embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0026] Example 1

[0027] A high-brightness photochromic polyester yarn comprises a skin layer and a core layer, wherein the mass ratio of the skin layer to the core layer is 1:6; the raw materials for preparing the skin layer comprise a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphonium bromide and methyl methacrylate in a mass ratio of 1:0.8:1; the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 5 parts of photochromic masterbatch, 3 parts of W-Mo-Ti-rare earth-BO, 3 parts of 2,4-diaminobenzenesulfonic acid, 0.8 parts of phosphorus pentoxide, 0.5 parts of polyphosphoric acid, 3 parts of antistatic agent and 1 part of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole.

[0028] The preparation method of the Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the antistatic agent is produced by BASF P18 FCA antistatic agent.

[0029] The preparation method of W-Mo-Ti-rare earth-BO comprises the following steps: dispersing a tungsten source, a molybdenum source, a titanium source, a rare earth source and a boron source in ethanol, stirring evenly, slowly adding sodium acetate, mixing evenly again to obtain a mixture, transferring the mixture to a hydrothermal reactor lined with polytetrafluoroethylene, and reacting at 195°C for 15 hours; cooling to room temperature, repeatedly washing with anhydrous ethanol, drying to constant weight in a vacuum drying oven at 80°C, grinding and sieving, and roasting at 600°C for 4 hours to obtain W-Mo-Ti-rare earth-BO; the tungsten source is sodium tungstate; the molybdenum source is molybdenum nitrate; the titanium source is titanium chloride; the rare earth source is lanthanum nitrate; the boron source is sodium borate; and the mass ratio of the tungsten source, the molybdenum source, the titanium source, the rare earth source, the boron source, ethanol and sodium acetate is 1:0.8:0.3:0.03:0.005:10:3.

[0030] The photochromic masterbatch is SunPercept from Suzhou Polydi Material Technology Co., Ltd. TM Ultra series red photochromic masterbatch; the polyester chips are industrial yarn-specific polyester chips 224 produced by Sinopec.

[0031] The preparation method of the copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyl triphenylphosphine bromide, methyl methacrylate and azobisisobutyronitrile to N,N-dimethylformamide, stirring and reacting for 3 hours at 60°C in a nitrogen atmosphere, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 3 times, and finally drying in a vacuum drying oven at 85°C to constant weight to obtain the copolymer; the mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, azobisisobutyronitrile and N,N-dimethylformamide is 1:0.03:10; through GPC test, the number average molecular weight of the copolymer is 16319 g / mol, M W / M n =1.319; calculated by elemental analysis and weight change, the mass ratio of the structural units introduced by 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphonium bromide and methyl methacrylate is 0.98:0.79:1.

[0032] A method for preparing the high-brightness photochromic polyester yarn comprises the following steps: firstly, vacuum drying the raw materials, uniformly mixing the raw materials of the core layer by weight and extruding the core layer material melt through a screw extruder, and extruding the copolymer through a screw extruder to obtain the skin layer material melt; the skin layer material melt and the core layer material melt are metered by respective metering pumps and enter a composite spinning box, and then are spun through a skin-core composite spinning assembly to obtain the high-brightness photochromic polyester yarn; the spinning temperature is 230°C, the cooling air temperature is 15°C, the initial spinning speed is 2000m / min, and the stretching multiple is 2.

[0033] A use of the high-brightness photochromic polyester yarn in preparing photochromic polyester fabrics.

[0034] Example 2

[0035] A high-brightness photochromic polyester yarn comprises a skin layer and a core layer, wherein the mass ratio of the skin layer to the core layer is 1:6.5; the raw materials for preparing the skin layer comprise a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide and methyl methacrylate in a mass ratio of 1:0.9:1.2; and the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 6 parts of photochromic masterbatch, 3.5 parts of W-Mo-Ti-rare earth-BO, 3.5 parts of 2,4-diaminobenzenesulfonic acid, 0.9 parts of phosphorus pentoxide, 0.6 parts of polyphosphoric acid, 3.5 parts of antistatic agent and 1.5 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole.

[0036] The preparation method of the Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the antistatic agent is produced by BASF P16 antistatic agent.

[0037] The preparation method of W-Mo-Ti-rare earth-BO comprises the following steps: dispersing a tungsten source, a molybdenum source, a titanium source, a rare earth source and a boron source in ethanol, stirring evenly, slowly adding sodium acetate, mixing evenly again to obtain a mixture, transferring the mixture to a hydrothermal reactor lined with polytetrafluoroethylene, and reacting at 200°C for 17 hours; cooling to room temperature, repeatedly washing with anhydrous ethanol, drying to constant weight in a vacuum drying oven at 83°C, grinding and sieving, and calcining at 650°C for 4.5 hours to obtain W-Mo-Ti-rare earth-BO; the tungsten source is sodium tungstate; the molybdenum source is molybdenum nitrate; the titanium source is titanium chloride; the rare earth source is cerium nitrate; the boron source is sodium borate; and the mass ratio of the tungsten source, the molybdenum source, the titanium source, the rare earth source, the boron source, ethanol and sodium acetate is 1:0.9:0.35:0.03:0.005:13:3.

[0038] The photochromic masterbatch is SunPercept from Suzhou Polydi Material Technology Co., Ltd. TM Ultra series red photochromic masterbatch; the polyester chips are industrial yarn-specific polyester chips 224 produced by Sinopec.

[0039] The preparation method of the copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide, methyl methacrylate and azobisisobutyronitrile to N,N-dimethylformamide, stirring and reacting for 4 hours at 63°C in a nitrogen atmosphere, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 4 times, and finally drying in a vacuum drying oven at 87°C to constant weight to obtain the copolymer; the mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, azobisisobutyronitrile and N,N-dimethylformamide is 1:0.035:12.

[0040] A method for preparing the high-brightness photochromic polyester yarn comprises the following steps: firstly, vacuum drying the raw materials, uniformly mixing the raw materials of the core layer by weight and extruding the core layer material melt through a screw extruder, and extruding the copolymer through a screw extruder to obtain the skin layer material melt; the skin layer material melt and the core layer material melt are metered by respective metering pumps and enter a composite spinning box, and then are spun through a skin-core composite spinning assembly to obtain the high-brightness photochromic polyester yarn; the spinning temperature is 245°C, the cooling air temperature is 17°C, the initial spinning speed is 2300m / min, and the stretching multiple is 2.

[0041] A use of the high-brightness photochromic polyester yarn in preparing photochromic polyester fabrics.

[0042] Example 3

[0043] A high-brightness photochromic polyester yarn comprises a skin layer and a core layer, wherein the mass ratio of the skin layer to the core layer is 1:7; the raw materials for preparing the skin layer comprise a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide and methyl methacrylate in a mass ratio of 1:1:1.5; the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 9 parts of photochromic masterbatch, 4 parts of W-Mo-Ti-rare earth-BO, 4 parts of 2,4-diaminobenzenesulfonic acid, 1 part of phosphorus pentoxide, 0.65 parts of polyphosphoric acid, 4 parts of antistatic agent and 2 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole.

[0044] The preparation method of the Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the antistatic agent is produced by BASF P20 antistatic agent.

[0045] The preparation method of W-Mo-Ti-rare earth-BO comprises the following steps: dispersing a tungsten source, a molybdenum source, a titanium source, a rare earth source and a boron source in ethanol, stirring evenly, slowly adding sodium acetate, mixing evenly again to obtain a mixture, transferring the mixture to a hydrothermal reactor lined with polytetrafluoroethylene, and reacting at 205°C for 19 hours; cooling to room temperature, repeatedly washing with anhydrous ethanol, drying to constant weight in a vacuum drying oven at 85°C, grinding and sieving, and roasting at 750°C for 5 hours to obtain W-Mo-Ti-rare earth-BO; the tungsten source is sodium tungstate; the molybdenum source is molybdenum nitrate; the titanium source is titanium chloride; the rare earth source is lanthanum nitrate; the boron source is sodium borate; and the mass ratio of the tungsten source, the molybdenum source, the titanium source, the rare earth source, the boron source, ethanol and sodium acetate is 1:1:0.4:0.03:0.005:15:3.

[0046] The photochromic masterbatch is SunPercept from Suzhou Polydi Material Technology Co., Ltd. TM Ultra series red photochromic masterbatch; the polyester chips are industrial yarn-specific polyester chips 224 produced by Sinopec.

[0047] The preparation method of the copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide, methyl methacrylate and azobisisobutyronitrile to N,N-dimethylformamide, stirring and reacting for 4.5 hours at 65°C in a nitrogen atmosphere, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 90°C to constant weight to obtain the copolymer; the mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, azobisisobutyronitrile and N,N-dimethylformamide is 1:0.04:15.

[0048] A preparation method of the high-brightness photochromic polyester yarn comprises the following steps: firstly, vacuum drying the raw materials, uniformly mixing the raw materials of the core layer by weight and extruding the core layer material melt through a screw extruder, and extruding the copolymer through a screw extruder to obtain the skin layer material melt; the skin layer material melt and the core layer material melt are metered by respective metering pumps and enter a composite spinning box, and then are spun through a skin-core composite spinning assembly to obtain the high-brightness photochromic polyester yarn; the spinning temperature is 260°C, the cooling air temperature is 17°C, the initial spinning speed is 2500m / min, and the stretching multiple is 2-3.

[0049] A use of the high-brightness photochromic polyester yarn in preparing photochromic polyester fabrics.

[0050] Example 4

[0051] A high-brightness photochromic polyester yarn comprises a skin layer and a core layer, wherein the mass ratio of the skin layer to the core layer is 1:7.5; the raw materials for preparing the skin layer comprise a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propylene)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide and methyl methacrylate in a mass ratio of 1:1.1:1.8; and the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 11 parts of photochromic masterbatch, 4.5 parts of W-Mo-Ti-rare earth-BO, 4.5 parts of 2,4-diaminobenzenesulfonic acid, 1.1 parts of phosphorus pentoxide, 0.75 parts of polyphosphoric acid, 4.5 parts of antistatic agent and 2.5 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole.

[0052] The preparation method of the Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the antistatic agent is produced by BASF P18 FCA antistatic agent, P16 antistatic agent, P20 antistatic agent is mixed in a mass ratio of 1:1:2.

[0053] The preparation method of W-Mo-Ti-rare earth-BO comprises the following steps: dispersing a tungsten source, a molybdenum source, a titanium source, a rare earth source and a boron source in ethanol, stirring evenly, slowly adding sodium acetate, mixing evenly again to obtain a mixture, transferring the mixture to a hydrothermal reactor lined with polytetrafluoroethylene, and reacting at 213°C for 21 hours; cooling to room temperature, repeatedly washing with anhydrous ethanol, drying to constant weight in a vacuum drying oven at 88°C, grinding and sieving, and roasting at 830°C for 5.5 hours to obtain W-Mo-Ti-rare earth-BO; the tungsten source is sodium tungstate; the molybdenum source is molybdenum nitrate; the titanium source is titanium chloride; the rare earth source is lanthanum nitrate; the boron source is sodium borate; and the mass ratio of the tungsten source, the molybdenum source, the titanium source, the rare earth source, the boron source, ethanol and sodium acetate is 1:1.1:0.45:0.03:0.005:18:3.

[0054] The photochromic masterbatch is SunPercept from Suzhou Polydi Material Technology Co., Ltd. TM Ultra series red photochromic masterbatch; the polyester chips are industrial yarn-specific polyester chips 224 produced by Sinopec.

[0055] The preparation method of the copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide, methyl methacrylate and azobisisobutyronitrile to N,N-dimethylformamide, stirring and reacting for 5.5 hours at 68°C in a nitrogen atmosphere, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying in a vacuum drying oven at 93°C to constant weight to obtain the copolymer; the mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, azobisisobutyronitrile and N,N-dimethylformamide is 1:0.045:18.

[0056] A method for preparing the high-brightness photochromic polyester yarn comprises the following steps: firstly, vacuum drying the raw materials, uniformly mixing the raw materials of the core layer by weight and extruding the core layer material melt through a screw extruder, and extruding the copolymer through a screw extruder to obtain the skin layer material melt; the skin layer material melt and the core layer material melt are metered by respective metering pumps and enter a composite spinning box, and then are spun through a skin-core composite spinning assembly to obtain the high-brightness photochromic polyester yarn; the spinning temperature is 270°C, the cooling air temperature is 19°C, the initial spinning speed is 2900m / min, and the stretching multiple is 2.

[0057] A use of the high-brightness photochromic polyester yarn in preparing photochromic polyester fabrics.

[0058] Example 5

[0059] A high-brightness photochromic polyester yarn comprises a skin layer and a core layer, wherein the mass ratio of the skin layer to the core layer is 1:(6-8); the raw materials for preparing the skin layer comprise a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propylene)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide and methyl methacrylate in a mass ratio of 1:1.2:2; the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 12 parts of photochromic masterbatch, 5 parts of W-Mo-Ti-rare earth-BO, 5 parts of 2,4-diaminobenzenesulfonic acid, 1.2 parts of phosphorus pentoxide, 0.8 parts of polyphosphoric acid, 5 parts of antistatic agent and 3 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole.

[0060] The preparation method of the Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenyl-calix[4]pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the antistatic agent is produced by BASF P18 FCA antistatic agent.

[0061] The preparation method of W-Mo-Ti-rare earth-BO comprises the following steps: dispersing a tungsten source, a molybdenum source, a titanium source, a rare earth source and a boron source in ethanol, stirring evenly, slowly adding sodium acetate, mixing evenly again to obtain a mixture, transferring the mixture to a hydrothermal reactor lined with polytetrafluoroethylene, and reacting at 215°C for 22 hours; cooling to room temperature, repeatedly washing with anhydrous ethanol, drying to constant weight in a vacuum drying oven at 90°C, grinding and sieving, and roasting at 850°C for 6 hours to obtain W-Mo-Ti-rare earth-BO; the tungsten source is sodium tungstate; the molybdenum source is molybdenum nitrate; the titanium source is titanium chloride; the rare earth source is cerium nitrate; the boron source is sodium borate; and the mass ratio of the tungsten source, the molybdenum source, the titanium source, the rare earth source, the boron source, ethanol and sodium acetate is 1:1.2:0.5:0.03:0.005:20:3.

[0062] The photochromic masterbatch is SunPercept from Suzhou Polydi Material Technology Co., Ltd. TM Ultra series red photochromic masterbatch; the polyester chips are industrial yarn-specific polyester chips 224 produced by Sinopec.

[0063] The preparation method of the copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide, methyl methacrylate and azobisisobutyronitrile to N,N-dimethylformamide, stirring and reacting for 6 hours at 70°C in a nitrogen atmosphere, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying in a vacuum drying oven at 95°C to constant weight to obtain the copolymer; the mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, azobisisobutyronitrile and N,N-dimethylformamide is 1:0.05:20.

[0064] A method for preparing the high-brightness photochromic polyester yarn comprises the following steps: firstly, vacuum drying the raw materials, uniformly mixing the raw materials of the core layer by weight and extruding the core layer material melt through a screw extruder, and extruding the copolymer through a screw extruder to obtain the skin layer material melt; the skin layer material melt and the core layer material melt are metered by respective metering pumps and enter a composite spinning box, and then are spun through a skin-core composite spinning assembly to obtain the high-brightness photochromic polyester yarn; the spinning temperature is 280°C, the cooling air temperature is 20°C, the initial spinning speed is 3000m / min, and the stretching multiple is 2.

[0065] A use of the high-brightness photochromic polyester yarn in preparing photochromic polyester fabrics.

[0066] Comparative Example 1

[0067] A high-brightness photochromic polyester yarn and a preparation method and application thereof, which are basically the same as Example 1, except that allyl triphenylphosphine bromide and W-Mo-Ti-rare earth-BO are not added.

[0068] Comparative Example 2

[0069] A high-brightness photochromic polyester yarn and a preparation method and application thereof, which are basically the same as Example 1, except that 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole are not added.

[0070] The high brightness photochromic polyester yarn samples described in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests. The test results are shown in Table 1. The test method is as follows:

[0071] (1) Breaking strength: refer to GB / T14344-2022 "Test method for tensile properties of chemical fiber filaments" for tensile properties test.

[0072] (2) Antistatic property: The surface resistivity of each fabric was tested with reference to GB / T12703.4-2010 “Evaluation of electrostatic properties of textiles Part 4: Resistivity”. The larger the value, the lower the antistatic property.

[0073] (4) Brightness and anti-see-through property: A colorimeter is used to measure the L value in the color space value of the fabric, and the anti-see-through index of the fabric is calculated based on the brightness. The anti-see-through property is evaluated using the evaluation method in GB / T 42698-2023 "Testing and evaluation of anti-see-through properties of textiles".

[0074] (5) Photochromic performance test: Each product was tested for photochromic performance. A 500W xenon lamp was used as the light source for 5 minutes to observe whether there was any color change. The product was washed 20 times in a standard manner and then tested for photochromic performance again. The results showed that the photochromic performance before and after washing was the same as before. If there was no change in the photochromic performance before and after washing, and there was obvious color change, the product passed the test. Otherwise, the product failed.

[0075] As can be seen from Table 1, the high-brightness photochromic polyester yarn disclosed in the embodiment of the present invention has better antistatic properties, mechanical strength, brightness, anti-see-through properties and photochromic properties than the comparative example; the combined use of allyl triphenylphosphine bromide, W-Mo-Ti-rare earth-BO, 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole is beneficial to improving the above properties.

[0076] Table 1

[0077]

[0078] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the attached claims and their equivalents.

Claims

1. A high-brightness photochromic polyester yarn, characterized in that: The invention comprises a skin layer and a core layer, wherein the mass ratio of the skin layer to the core layer is 1:(6-8); the raw materials for preparing the skin layer comprise a copolymer prepared by free radical copolymerization of 1,3-bis(oxiranylmethyl)-5-(2-propylene)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide and methyl methacrylate in a mass ratio of 1:(0.8-1.2):(1-2); and the core layer is prepared from the following raw materials in parts by weight: 100 parts of polyester chips, 5-12 parts of photochromic masterbatch, 3-5 parts of W-Mo-Ti-rare earth-BO, 3-5 parts of 2,4-diaminobenzenesulfonic acid, 0.8-1.2 parts of phosphorus pentoxide, 0.5-0.8 parts of polyphosphoric acid, 3-5 parts of antistatic agent and 1-3 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole.

2. The high-brightness photochromic polyester yarn according to claim 1, characterized in that: The antistatic agent is produced by BASF P18 FCA antistatic agent, P16 antistatic agent, At least one of P20 antistatic agents.

3. The high-brightness photochromic polyester yarn according to claim 1, characterized in that: The preparation method of W-Mo-Ti-rare earth-BO comprises the following steps: dispersing a tungsten source, a molybdenum source, a titanium source, a rare earth source and a boron source in ethanol, stirring evenly, slowly adding sodium acetate, mixing evenly again to obtain a mixture, transferring the mixture to a hydrothermal reactor lined with polytetrafluoroethylene, reacting at 195-215°C for 15-22h; cooling to room temperature, repeatedly washing with anhydrous ethanol, drying to constant weight in a vacuum drying oven at 80-90°C, grinding and sieving, and roasting at 600-850°C for 4-6h to obtain W-Mo-Ti-rare earth-BO.

4. The high-brightness photochromic polyester yarn according to claim 3, characterized in that: The tungsten source is sodium tungstate; the molybdenum source is molybdenum nitrate; the titanium source is titanium chloride; the rare earth source is at least one of lanthanum nitrate and cerium nitrate; and the boron source is sodium borate.

5. The high-brightness photochromic polyester yarn according to claim 3, characterized in that: The mass ratio of the tungsten source, molybdenum source, titanium source, rare earth source, boron source, ethanol and sodium acetate is 1:(0.8-1.2):(0.3-0.5):0.03:0.005:(10-20):

3.

6. The high-brightness photochromic polyester yarn according to claim 1, characterized in that: The photochromic masterbatch is SunPercept from Suzhou Polydi Material Technology Co., Ltd. TM Ultra series red photochromic masterbatch; the polyester chips are industrial yarn-specific polyester chips 224 produced by Sinopec.

7. The high-brightness photochromic polyester yarn according to claim 1, characterized in that: The preparation method of the copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, allyltriphenylphosphine bromide, methyl methacrylate and azobisisobutyronitrile to N,N-dimethylformamide, stirring and reacting for 3-6 hours at 60-70°C in a nitrogen atmosphere, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 85-95°C to constant weight to obtain the copolymer; the mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, azobisisobutyronitrile and N,N-dimethylformamide is 1:(0.03-0.05):(10-20).

8. A method for preparing the high-brightness photochromic polyester yarn according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: firstly, vacuum drying the raw materials, uniformly mixing the raw materials of the core layer by weight, extruding the core layer material melt through a screw extruder, and extruding the copolymer through a screw extruder to obtain the skin layer material melt; the skin layer material melt and the core layer material melt are metered by respective metering pumps and enter a composite spinning box, and then are spun through a skin-core composite spinning assembly to obtain a high-brightness photochromic polyester yarn.

9. The method for preparing high-brightness photochromic polyester yarn according to claim 8, characterized in that: The spinning temperature is 230-280° C., the cooling air temperature is 15-20° C., the initial spinning speed is 2000-3000 m / min, and the stretching multiple is 2-3.

10. Use of the high-brightness photochromic polyester yarn according to any one of claims 1 to 7 in preparing photochromic polyester fabrics.

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