Organic / inorganic composite anti-ultraviolet extinction polyester masterbatch, preparation method and application thereof

Abstract

The invention relates to the technical field of polymer materials and discloses an organic / inorganic composite anti-ultraviolet extinction polyester masterbatch, a preparation method and an application thereof. The masterbatch comprises, by weight, 30-70 parts of a polyester matrix, 30-65 parts of an organic / inorganic composite anti-ultraviolet nanopowder, 0.01-1.0 parts of a light stabilizer, 0.05-2.0 parts of an antioxidant, and 0.2-2.0 parts of a dispersant. The organic / inorganic composite anti-ultraviolet nanopowder is an anti-ultraviolet material formed by compounding an inorganic anti-ultraviolet material and an organic ultraviolet absorber via a coupling agent and an initiator. The material is made of raw materials in a specific ratio, has multiple anti-ultraviolet effects, and can efficiently absorb ultraviolet rays. The preparation method has simple process and low cost, and the organic / inorganic composite anti-ultraviolet nanopowder added to the polyester matrix has good dispersibility. The prepared organic / inorganic composite anti-ultraviolet extinction polyester masterbatch is applied to spinning to obtain fibers with good mechanical properties and high anti-ultraviolet performance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to an organic / inorganic composite anti-ultraviolet extinction polyester masterbatch, a preparation method and application thereof. Background Art

[0002] Ultraviolet radiation can quickly cause materials to oxidize and degenerate, accelerate material aging, and reduce their durability. Therefore, in order to solve the above problems, the existing technology has developed many anti-UV materials, mainly including inorganic anti-UV materials and organic UV absorbers. Inorganic anti-UV materials can produce physical effects such as reflection and refraction on ultraviolet rays, thereby weakening or even isolating the damage of ultraviolet rays to the materials. The chemical groups in organic UV absorbers can absorb ultraviolet rays, thereby achieving the effect of preventing the material from being damaged by ultraviolet rays.

[0003] The raw material of synthetic fibers is organic polyester. After being exposed to ultraviolet rays, the chemical bonds between the fiber molecules of organic polyester fibers will break, causing the fibers to age and break. In the prior art, organic polyesters are modified with anti-ultraviolet materials so that the final synthetic fibers have anti-ultraviolet properties. For example, the nano-titanium nitride anti-ultraviolet polyester fiber disclosed in Publication No. CN100503910C blends inorganic nano-titanium nitride anti-ultraviolet masterbatch with polyester chips to impart anti-ultraviolet properties to the polyester fibers. Another example is the method for manufacturing anti-ultraviolet polyester fibers disclosed in Publication No. CN102031580A, which blends inorganic anti-ultraviolet masterbatch with organic anti-ultraviolet additives into polyester chips to improve the anti-ultraviolet properties of the polyester fibers.

[0004] The inorganic and organic UV-resistant materials used in the prior art are used separately, providing a single UV protection method and failing to effectively shield the polyester from UV damage. Furthermore, in actual production, adding both materials separately can be difficult to disperse, resulting in complex processes and high costs. Summary of the Invention

[0005] In order to overcome the problems existing in the above-mentioned prior art, the present application provides an organic / inorganic composite anti-UV extinction polyester masterbatch, a preparation method and its application. The masterbatch contains an organic / inorganic composite anti-UV nanopowder. The organic / inorganic composite anti-UV nanopowder is an anti-UV material formed by compounding an inorganic anti-UV material and an organic UV absorber via a coupling agent and an initiator. The material is made of raw materials in a specific proportion and has multiple anti-UV effects. In addition, the material has little effect on the mechanical properties of polyester fibers when added to polyester, and the process is simple and the cost is low.

[0006] The specific technical solutions of the present invention are:

[0007] An organic / inorganic composite anti-ultraviolet matting polyester masterbatch, comprising, by parts by mass:

[0008] 30-70 parts of polyester matrix;

[0009] 30-65 parts of organic / inorganic composite anti-ultraviolet nanomaterials;

[0010] Light stabilizer 0.01-1.0 part;

[0011] 0.05-2.0 parts of antioxidant;

[0012] Dispersant 0.2-2.0 parts.

[0013] The organic / inorganic composite anti-ultraviolet nanomaterial comprises the following preparation steps:

[0014] The inorganic anti-ultraviolet material, coupling agent, ultraviolet absorber and initiator are reacted in a mass ratio of 90-98:0.2-3.0:2.0-5.0:0.1-2.0 to prepare an organic / inorganic composite anti-ultraviolet nanometer material.

[0015] Preferably, the inorganic anti-ultraviolet material is titanium dioxide, and the particle size of the titanium dioxide is 100 to 500 nm.

[0016] Preferably, the coupling agent is selected from one or more of vinyltrimethoxysilane (A-171), vinyltri(β-methoxyethoxy) (A-172), γ-(methacryloyloxy)propyltrimethoxysilane (A-174) and vinyltriethoxysilane (A-151).

[0017] Preferably, the UV absorber is selected from one or more of 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole, 2-hydroxy-4-(3-methacrylate-2-hydroxypropoxy)benzophenone and 2-hydroxy-4-methacrylate benzophenone.

[0018] Preferably, the initiator is selected from azobisisobutyronitrile (AIBN) and / or benzoyl peroxide (BPO).

[0019] The present application provides an organic / inorganic composite anti-ultraviolet matt polyester masterbatch, which includes an organic / inorganic composite anti-ultraviolet nanomaterial, which is a special structural material made of an inorganic anti-ultraviolet material, a coupling agent, an ultraviolet absorber and an initiator in a specific proportion; one end of the coupling agent contains a double bond and the other end contains a silane group, the double bond of the coupling agent can react with the ultraviolet absorber having a double bond under the action of the initiator, and the silane group of the coupling agent can undergo a cross-linking reaction with the hydroxyl group on the surface of the inorganic anti-ultraviolet material, thereby modifying the ultraviolet absorber on the surface of the inorganic anti-ultraviolet absorber and forming a special structure with the inorganic ultraviolet absorber as the core and the anti-ultraviolet absorber as the shell. During the use of organic / inorganic composite anti-UV extinction polyester masterbatch, ultraviolet rays first need to pass through the cross-linked network shell formed by the anti-UV absorber. Part of the ultraviolet rays are absorbed by the ultraviolet absorber, and the other part is irradiated onto the inorganic ultraviolet absorber core through the gaps in the network. The inorganic anti-UV material core reflects the ultraviolet rays back to the cross-linked network shell of the anti-UV absorber and is absorbed by the ultraviolet absorber. Through multiple anti-UV effects, it can efficiently absorb ultraviolet rays and prevent ultraviolet rays from overflowing, and can extremely effectively shield the destructive effects of ultraviolet rays on polyester masterbatch.

[0020] Furthermore, the reaction steps are: placing the inorganic anti-ultraviolet material in an organic solvent, heating, stirring, and ultrasonically dispersing to form a mixture, the heating temperature being 40 to 80°C, and then injecting a coupling agent, an ultraviolet absorber, and an initiator into the mixture to react for 2 to 6 hours. After the reaction is completed, centrifugation is performed to remove the precipitate, and then the precipitate is washed, dried, and ground to form an organic / inorganic composite anti-ultraviolet nanomaterial.

[0021] A method for preparing an organic / inorganic composite anti-ultraviolet matting polyester masterbatch comprises the following steps:

[0022] The polyester matrix, the organic / inorganic composite anti-ultraviolet nanometer material, the light stabilizer, the antioxidant and the dispersant are mixed and kneaded and extruded to prepare the organic / inorganic composite anti-ultraviolet extinction polyester masterbatch.

[0023] Preferably, the polyester matrix is ​​selected from one or more of polyethylene terephthalate (PET), polypropylene terephthalate (PTT) and polybutylene terephthalate (PBT);

[0024] Preferably, the light stabilizer is 2,2-thiobis(4-tert-octylphenol) n-butylamine nickel salt (UV-1084);

[0025] Preferably, the antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010) and / or tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168);

[0026] Preferably, the dispersant is selected from one or more of white oil, calcium stearate, low-density homopolymer wax, ethylene acrylic acid copolymer and maleic anhydride graft.

[0027] Furthermore, the mixing conditions include: a mixing speed of 1000 to 3000 r / min and a mixing time of 20 to 40 min; the kneading conditions include: a kneading extrusion temperature of 210 to 250° C. and a kneading extrusion speed of 300 to 600 r / min.

[0028] This application also provides a method for preparing an organic / inorganic composite anti-UV matting polyester masterbatch. This method has a simple preparation process and low cost. Furthermore, the organic / inorganic composite anti-UV nanomaterial has good dispersibility when added to a polyester matrix, and the resulting organic / inorganic composite anti-UV matting polyester masterbatch has excellent mechanical properties and high UV resistance.

[0029] Application of an organic / inorganic composite anti-ultraviolet extinction polyester masterbatch or a preparation method of an organic / inorganic composite anti-ultraviolet extinction polyester masterbatch.

[0030] Compared with the existing technology, this application has the following technical effects:

[0031] (1) The organic / inorganic composite anti-ultraviolet nanomaterial provided by this application is an anti-ultraviolet material formed by compounding an inorganic anti-ultraviolet material and an organic ultraviolet absorber via a coupling agent and an initiator. The material is made of raw materials in a specific ratio, has multiple anti-ultraviolet effects, and can efficiently absorb ultraviolet rays;

[0032] (2) The preparation method provided by the present application has a simple process and low cost, and the organic / inorganic composite anti-ultraviolet nanomaterial added to the polyester matrix has good dispersion. The prepared organic / inorganic composite anti-ultraviolet extinction polyester masterbatch has good mechanical properties and high anti-ultraviolet performance. DETAILED DESCRIPTION

[0033] The present invention will be further described below with reference to the embodiments.

[0034] Example 1:

[0035] An organic / inorganic composite anti-ultraviolet matting polyester masterbatch, comprising, by parts by mass:

[0036] 60 parts of polyester matrix, the polyester matrix is ​​PET chips;

[0037] 35 parts of organic / inorganic composite anti-UV nanopowder;

[0038] 0.2 parts of light stabilizer, the light stabilizer is UV-1084;

[0039] 0.3 parts of antioxidant, antioxidant 1010;

[0040] 2.0 parts of dispersant, which is white oil;

[0041] The organic / inorganic composite anti-ultraviolet nanomaterial comprises the following preparation steps:

[0042] The inorganic anti-ultraviolet material was dispersed in an organic solvent, ultrasonically dispersed for 30 minutes, heated and stirred at 60°C, and then a coupling agent, an organic ultraviolet absorber, and an initiator were added respectively; after reacting for 4 hours, the precipitate was removed by centrifugation, washed with water and alcohol, dried in a vacuum oven at 80°C for 24 hours, and finally ground to obtain an organic / inorganic composite anti-ultraviolet nanomaterial;

[0043] The mass ratio of the inorganic anti-ultraviolet material, the coupling agent, the organic ultraviolet absorber and the initiator is 97:0.2:2.0:0.8;

[0044] The inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 200nm;

[0045] The organic solvent is ethanol;

[0046] The coupling agent is A-172;

[0047] The organic UV absorber is 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole;

[0048] The initiator is AIBN;

[0049] A method for preparing an organic / inorganic composite anti-ultraviolet matting polyester masterbatch comprises the following steps:

[0050] According to the above-mentioned organic / inorganic composite anti-UV extinction polyester masterbatch formula ratio, the dried polyester matrix, organic / inorganic composite anti-UV nanopowder, light stabilizer, antioxidant and dispersant are added to a high-speed mixer for mixing, and the obtained mixed powder is transported by a feeding system to a twin-screw extruder for dispersion, mixing, extrusion and granulation to obtain the organic / inorganic composite anti-UV extinction polyester masterbatch; the speed of the high-speed mixer is 2000 r / min, and the mixing time is 30 min; the temperature of the twin-screw extruder is 220°C and the speed is 500 r / min.

[0051] Example 2:

[0052] An organic / inorganic composite anti-ultraviolet matting polyester masterbatch, comprising, by parts by mass:

[0053] 65 parts of polyester matrix, which is composed of PET chips and PBT chips, with the mass ratio of PET chips to PBT chips being 8:2; 30 parts of organic / inorganic composite anti-UV nanopowder;

[0054] 0.5 parts of light stabilizer, the light stabilizer is UV-1084;

[0055] 0.5 parts of antioxidant, the antioxidants are antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1;

[0056] 1.0 part of dispersant, the dispersant is ethylene acrylic acid copolymer;

[0057] The organic / inorganic composite anti-ultraviolet nanomaterial comprises the following preparation steps:

[0058] The inorganic anti-ultraviolet material was dispersed in an organic solvent, ultrasonically dispersed for 30 minutes, heated and stirred at 60°C, and then a coupling agent, an organic ultraviolet absorber and an initiator were added respectively; after reacting for 4 hours, the precipitate was taken out by centrifugation, washed with water and alcohol, dried in a vacuum oven at 80°C for 24 hours, and finally ground to obtain an organic / inorganic composite anti-ultraviolet nanomaterial;

[0059] The mass ratio of the inorganic anti-ultraviolet material, coupling agent, organic ultraviolet absorber and initiator is 95:2.0:2.0:1.0;

[0060] The inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 200nm;

[0061] The organic solvent is ethanol; the coupling agent is A-172;

[0062] The organic UV absorber is 2-hydroxy 4-(3-methacrylate-2-hydroxypropoxy) benzophenone;

[0063] The initiator is AIBN;

[0064] A method for preparing an organic / inorganic composite anti-ultraviolet matting polyester masterbatch comprises the following steps:

[0065] According to the above-mentioned organic / inorganic composite anti-UV extinction polyester masterbatch formula ratio, the dried polyester matrix, organic / inorganic composite anti-UV nanopowder, light stabilizer, antioxidant and dispersant are added to a high-speed mixer for mixing, and the obtained mixed powder is transported by a feeding system to a twin-screw extruder for dispersion, mixing, extrusion and granulation to obtain the organic / inorganic composite anti-UV extinction polyester masterbatch; the speed of the high-speed mixer is 2500 r / min, and the mixing time is 40 min; the temperature of the twin-screw extruder is 215°C and the speed is 400 r / min.

[0066] Example 3:

[0067] An organic / inorganic composite anti-ultraviolet matting polyester masterbatch, comprising, by parts by mass:

[0068] 50 parts of polyester matrix, the polyester matrix is ​​PTT slices;

[0069] 40 parts of organic / inorganic composite anti-UV nanopowder;

[0070] 1.0 part of light stabilizer, light stabilizer is UV-1084;

[0071] 1.0 part of antioxidant, wherein the antioxidants are antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:2;

[0072] 3.0 parts of dispersant, which is a low-density homopolymer wax;

[0073] The organic / inorganic composite anti-ultraviolet nanomaterial comprises the following preparation steps:

[0074] The inorganic anti-ultraviolet material was dispersed in an organic solvent, ultrasonically dispersed for 30 minutes, heated and stirred at 40°C, and then a coupling agent, an organic ultraviolet absorber and an initiator were added respectively; after reacting for 6 hours, the precipitate was taken out by centrifugation, washed with water and alcohol, dried in a vacuum oven at 80°C for 24 hours, and finally ground to obtain an organic / inorganic composite anti-ultraviolet nanomaterial;

[0075] The mass ratio of the inorganic anti-ultraviolet material, coupling agent, organic ultraviolet absorber and initiator is 95:2.0:2.0:1.0;

[0076] The inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 300nm;

[0077] The organic solvent is ethanol; the coupling agent is A-172;

[0078] The organic UV absorber is 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole;

[0079] The initiator is BPO;

[0080] A method for preparing an organic / inorganic composite anti-ultraviolet matting polyester masterbatch comprises the following steps:

[0081] According to the above-mentioned organic / inorganic composite anti-UV extinction polyester masterbatch formula ratio, the dried polyester matrix, organic / inorganic composite anti-UV nanopowder, light stabilizer, antioxidant and dispersant are added to a high-speed mixer for mixing, and the obtained mixed powder is transported by a feeding system to a twin-screw extruder for dispersion, mixing, extrusion and granulation to obtain an organic / inorganic composite anti-UV extinction polyester masterbatch; the speed of the high-speed mixer is 2000 r / min, and the mixing time is 30 min; the temperature of the twin-screw extruder is 215°C, and the speed is 500 r / min.

[0082] Example 4:

[0083] An organic / inorganic composite anti-ultraviolet matting polyester masterbatch, comprising, by parts by mass:

[0084] 50 parts of polyester matrix, the polyester matrix is ​​PET chips;

[0085] 40 parts of organic / inorganic composite anti-UV nanopowder;

[0086] 1.0 part of light stabilizer, light stabilizer is UV-1084;

[0087] 1.0 part of antioxidant, wherein the antioxidants are antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:2;

[0088] 3.0 parts of a dispersant, wherein the dispersant is a low-density homopolymer wax and an ethylene acrylic acid copolymer, and the mass ratio of the low-density homopolymer wax and the ethylene acrylic acid copolymer is 1:1;

[0089] The organic / inorganic composite anti-ultraviolet nanomaterial comprises the following preparation steps:

[0090] The inorganic anti-ultraviolet material was dispersed in an organic solvent, ultrasonically dispersed for 30 minutes, heated and stirred at 60°C, and then a coupling agent, an organic ultraviolet absorber and an initiator were added respectively; after reacting for 4 hours, the precipitate was taken out by centrifugation, washed with water and alcohol, dried in a vacuum oven at 80°C for 24 hours, and finally ground to obtain an organic / inorganic composite anti-ultraviolet nanomaterial;

[0091] The mass ratio of the inorganic anti-ultraviolet material, the coupling agent, the organic ultraviolet absorber and the initiator is 94:2.0:3.0:1.0;

[0092] The inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 300nm;

[0093] The organic solvent is ethanol;

[0094] The coupling agent is A-172;

[0095] The organic UV absorber is 2-hydroxy-4-methacrylate benzophenone;

[0096] The initiator is AIBN;

[0097] A method for preparing an organic / inorganic composite anti-ultraviolet matting polyester masterbatch comprises the following steps:

[0098] According to the above-mentioned organic / inorganic composite anti-UV extinction polyester masterbatch formula ratio, the dried polyester matrix, organic / inorganic composite anti-UV nanopowder, light stabilizer, antioxidant and dispersant are added to a high-speed mixer for mixing, and the obtained mixed powder is transported by a feeding system to a twin-screw extruder for dispersion, mixing, extrusion and granulation to obtain the organic / inorganic composite anti-UV extinction polyester masterbatch; the speed of the high-speed mixer is 2000 r / min, and the mixing time is 40 min; the temperature of the twin-screw extruder is 220°C and the speed is 400 r / min.

[0099] Example 5:

[0100] An organic / inorganic composite anti-ultraviolet matting polyester masterbatch, comprising, by parts by mass:

[0101] 50 parts of polyester matrix, which is composed of PET chips and PBT chips, with the mass ratio of PET chips to PBT chips being 8:2; 40 parts of organic / inorganic composite anti-UV nanopowder;

[0102] 1.0 part of light stabilizer, light stabilizer is UV-1084;

[0103] 1.0 part of antioxidant, wherein the antioxidants are antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1;

[0104] 3.0 parts of a dispersant, wherein the dispersant is an ethylene acrylic acid copolymer and a maleic anhydride graft, and the mass ratio of the ethylene acrylic acid copolymer to the maleic anhydride graft is 2:1;

[0105] The organic / inorganic composite anti-ultraviolet nanomaterial comprises the following preparation steps:

[0106] The inorganic anti-ultraviolet material is dispersed in an organic solvent, ultrasonically dispersed for 30 minutes, heated at 80°C with stirring, and then a coupling agent, an organic ultraviolet absorber, and an initiator are added respectively; after reacting for 2 hours, the precipitate is taken out by centrifugation, washed with water and alcohol, dried in a vacuum oven at 80°C for 24 hours, and finally ground to obtain an organic / inorganic composite anti-ultraviolet nanomaterial;

[0107] The mass ratio of the inorganic anti-ultraviolet material, the coupling agent, the organic ultraviolet absorber and the initiator is 96:1.0:2.5:0.5;

[0108] The inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 300nm;

[0109] The organic solvent is ethanol;

[0110] The coupling agent is A-151;

[0111] The organic UV absorber is 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole;

[0112] The initiator is BPO;

[0113] A method for preparing an organic / inorganic composite anti-ultraviolet matting polyester masterbatch comprises the following steps:

[0114] According to the above-mentioned organic / inorganic composite anti-UV extinction polyester masterbatch formula ratio, the dried polyester matrix, organic / inorganic composite anti-UV nanopowder, light stabilizer, antioxidant and dispersant are added to a high-speed mixer for mixing, and the obtained mixed powder is transported by a feeding system to a twin-screw extruder for dispersion, mixing, extrusion and granulation to obtain the organic / inorganic composite anti-UV extinction polyester masterbatch; the speed of the high-speed mixer is 3000 r / min, and the mixing time is 30 min; the temperature of the twin-screw extruder is 215°C and the speed is 400 r / min.

[0115] Example 6:

[0116] An organic / inorganic composite anti-ultraviolet matting polyester masterbatch, comprising, by parts by mass:

[0117] 50 parts of polyester matrix, the polyester matrix is ​​PTT slices;

[0118] 45 parts of organic / inorganic composite anti-UV nanopowder;

[0119] 1.0 part of light stabilizer, light stabilizer is UV-1084;

[0120] 0.5 parts of antioxidant, the antioxidants are antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1;

[0121] 1.0 part of dispersant, which is a maleic anhydride grafted compound;

[0122] The organic / inorganic composite anti-ultraviolet nanomaterial comprises the following preparation steps:

[0123] The inorganic anti-ultraviolet material is dispersed in an organic solvent, ultrasonically dispersed for 30 minutes, heated at 80°C with stirring, and then a coupling agent, an organic ultraviolet absorber, and an initiator are added respectively; after reacting for 2 hours, the precipitate is taken out by centrifugation, washed with water and alcohol, dried in a vacuum oven at 80°C for 24 hours, and finally ground to obtain an organic / inorganic composite anti-ultraviolet nanomaterial;

[0124] The mass ratio of the inorganic anti-ultraviolet material, coupling agent, organic ultraviolet absorber and initiator is 96:1.0:2.5:0.5;

[0125] The inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 200nm;

[0126] The organic solvent is ethanol;

[0127] The coupling agent is A-171;

[0128] The organic UV absorber is 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole;

[0129] The initiator is BPO;

[0130] A method for preparing an organic / inorganic composite anti-ultraviolet matting polyester masterbatch comprises the following steps:

[0131] According to the above-mentioned organic / inorganic composite anti-UV extinction polyester masterbatch formula ratio, the dried polyester matrix, organic / inorganic composite anti-UV nanopowder, light stabilizer, antioxidant and dispersant are added to a high-speed mixer for mixing, and the obtained mixed powder is transported by a feeding system to a twin-screw extruder for dispersion, mixing, extrusion and granulation to obtain an organic / inorganic composite anti-UV extinction polyester masterbatch; the speed of the high-speed mixer is 2000 r / min, and the mixing time is 40 min; the temperature of the twin-screw extruder is 220°C and the speed is 500 r / min.

[0132] Comparative Example 1: (Inorganic anti-ultraviolet material)

[0133] Compared with Example 1, the masterbatch formula in Comparative Example 1 uses inorganic nano-titanium dioxide and does not use organic / inorganic composite anti-ultraviolet nano-powder. The other conditions are the same as those in Example 1.

[0134] Comparative Example 2: (Organic UV Absorber)

[0135] Compared with Example 1, the masterbatch formula in Comparative Example 2 uses the organic UV absorber 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole, and does not use the organic / inorganic composite anti-UV nanopowder. The other conditions are the same as those in Example 1.

[0136] Comparative Example 3: (Inorganic anti-ultraviolet material mixed with organic ultraviolet absorber)

[0137] Compared with Example 1, the masterbatch formula in Comparative Example 3 uses inorganic nano-titanium dioxide and an organic UV absorber 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole, and does not use an organic / inorganic composite anti-UV nanopowder. Inorganic nano-titanium dioxide and an organic UV absorber are added separately in the preparation method, and the other conditions are the same as those in Example 1.

[0138] Test example

[0139] The UV-resistant polyester masterbatch prepared in Examples 1 to 6 and Comparative Examples 1 to 3 is applied to polyester fiber spinning, comprising the following steps: drying the UV-resistant polyester masterbatch and conventional PET chips at 120° C. for 20 h, mixing them uniformly in a mass ratio of 1:22, and then spinning them at a spinning temperature of 260 to 285° C. to produce UV-resistant polyester fibers, with the draft ratio controlled at 3.5 to 4.5.

[0140] The ultraviolet protection factor (UPF) and mechanical properties (breaking strength and breaking elongation) of the UV-resistant polyester fiber prepared above were tested. The ultraviolet protection factor test procedure was in accordance with GB / T 18830-2009, and the mechanical property test procedure was in accordance with GB / T 1040.2-2022. The test results are shown in Table 1.

[0141] Table 1 UPF value and mechanical properties of UV-resistant fibers

[0142] UPF value Breaking strength (cN / dtex) Elongation at break (%) Example 1 59.46 4.09 20.45 Example 2 58.48 3.96 21.06 Example 3 58.66 3.66 24.56 Example 4 58.47 3.73 23.52 Example 5 59.28 3.82 22.19 Example 6 58.84 3.68 24.28 Comparative Example 1 52.58 4.12 19.13 Comparative Example 2 46.34 3.73 31.45 Comparative Example 3 58.28 4.05 20.13

[0143] As shown in Table 1, the UPF values ​​of Examples 1 to 6 are significantly higher than those of Comparative Examples 1 to 2, and the UPF value of Example 1 is higher than that of Comparative Example 3. It can be seen from the above results that the organic / inorganic composite anti-UV nanomaterial provided by the present application can significantly improve the anti-UV performance of polyester fibers, and the anti-UV performance of the composite anti-UV nanomaterial is higher than that of a single anti-UV material and a simple combination of a single anti-UV material; in addition, it can be seen from the mechanical property results of Example 1 and Comparative Example 3 that the mechanical properties of the composite anti-UV nanomaterial are higher than those of a simple combination of a single anti-UV material. The reason for the above results is that the dispersion effect of the inorganic nanomaterial and the organic UV absorber added separately in the polyester matrix is ​​lower than the dispersion effect of the composite anti-UV nanomaterial in the polyester matrix; it can be seen from the UPF value results of Examples 1 to 6 that the ratio of the masterbatch will affect the anti-UV effect and mechanical properties of the final product fiber.

[0144] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. An organic / inorganic composite anti-ultraviolet extinction polyester masterbatch, characterized in that: Included by mass: 30-70 parts of polyester matrix; 30-65 parts of organic / inorganic composite anti-UV nanopowder; Light stabilizer 0.01~1.0 part; Antioxidant 0.05~2.0 parts; Dispersant 0.2~2.0 parts; The raw materials of the organic / inorganic composite anti-ultraviolet nanomaterial include: inorganic anti-ultraviolet material, coupling agent, ultraviolet absorber and initiator in a mass ratio of 90-98:0.2-3.0:2.0-5.0:0.1-2.0; The inorganic anti-ultraviolet material is titanium dioxide; The coupling agent is selected from vinyl trimethoxysilane, vinyl tri ( β -methoxyethoxy), γ -One or more of (methacryloyloxy)propyltrimethoxysilane and vinyltriethoxysilane; The ultraviolet absorber is selected from one or more of 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole, 2-hydroxy-4-(3-methacrylate-2-hydroxypropoxy)benzophenone and 2-hydroxy-4-methacrylate benzophenone.

2. The organic / inorganic composite anti-ultraviolet matting polyester masterbatch according to claim 1, characterized in that: The particle size of the titanium dioxide is 100-500 nm.

3. The organic / inorganic composite anti-ultraviolet extinction polyester masterbatch according to claim 1, characterized in that: The initiator is selected from azobisisobutyronitrile and / or benzoyl peroxide.

4. The organic / inorganic composite anti-ultraviolet matting polyester masterbatch according to claim 1, wherein the polyester matrix is ​​selected from one or more of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate.

5. The organic / inorganic composite anti-ultraviolet matting polyester masterbatch according to claim 1, characterized in that: The light stabilizer is 2,2-thiobis(4-tert-octylphenol) n-butylamine nickel salt.

6. The organic / inorganic composite anti-ultraviolet extinction polyester masterbatch according to claim 1, characterized in that: The antioxidant is selected from the group consisting of β [-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester and / or tris(2,4-di-tert-butylphenyl) phosphite.

7. The organic / inorganic composite anti-ultraviolet extinction polyester masterbatch according to claim 1, characterized in that: The dispersant is selected from one or more of white oil, calcium stearate, low-density homopolymer wax, ethylene acrylic acid copolymer and maleic anhydride graft.

8. A method for preparing the organic / inorganic composite anti-ultraviolet matting polyester masterbatch according to any one of claims 1 to 7, characterized in that: The method comprises the following preparation steps: mixing a polyester matrix, an organic / inorganic composite anti-ultraviolet nanometer material, a light stabilizer, an antioxidant and a dispersant, and kneading and extruding the mixture to prepare an organic / inorganic composite anti-ultraviolet extinction polyester masterbatch.

9. The preparation method according to claim 8, wherein The preparation method of the organic / inorganic composite anti-ultraviolet nanomaterial comprises the following steps: placing the inorganic anti-ultraviolet material in an organic solvent, heating, stirring, and ultrasonically dispersing the inorganic anti-ultraviolet material to form a mixture, the heating temperature being 40-80°C, injecting a coupling agent, an ultraviolet absorber, and an initiator into the mixture to react for 2-6 hours, and after the reaction is completed, centrifuging to remove the precipitate, and then washing, drying, and grinding the precipitate to form the organic / inorganic composite anti-ultraviolet nanomaterial.

10. The preparation method according to claim 8, wherein The mixing conditions include: a mixing speed of 1000-3000 r / min and a mixing time of 20-40 min; the kneading conditions include: a kneading extrusion temperature of 210-250°C and a kneading extrusion speed of 300-600 r / min.