Preparation method of surface hydrophobic modified nano inorganic powder and functional fiber

Abstract

The application relates to a preparation method of surface hydrophobic modified nano inorganic powder and functional fibers, and the preparation method of the modified nano inorganic powder comprises the following steps: firstly, heating and reacting nano inorganic powder and boric acid to obtain hydroxyl-activated nano inorganic powder; then, reacting the hydroxyl-activated nano inorganic powder with long carbon chain alkanol to obtain surface hydrophobic modified nano inorganic powder. The preparation method of the functional fibers comprises the following steps: melt blending and extruding the surface hydrophobic modified nano inorganic powder, polymer chips, a dispersing agent and an antioxidant to prepare functional master batches, and melt spinning to obtain the functional fibers. Compared with the prior art, the application can solve the problems that the nano inorganic powder is not uniformly dispersed in the organic polymer and is prone to agglomeration, so that the nano inorganic powder is uniformly dispersed in the fibers, and the comprehensive performance of the composite fibers is improved.

Description

Technical Field

[0001] This invention belongs to the field of materials technology and relates to a method for preparing surface-hydrophobically modified nano-inorganic powders and functional fibers. Background Technology

[0002] Nanoparticles, as important functional materials, play a crucial role in numerous fields. In the fiber industry, the application of nanoparticles brings many superior properties to fiber materials. For example, nanoparticles can improve the strength, wear resistance, and corrosion resistance of fibers, while also endowing them with special functions such as antibacterial properties, UV resistance, and thermal insulation. Furthermore, nanoparticles can improve the dyeing properties and hand feel of fibers, making them more comfortable and aesthetically pleasing.

[0003] However, nano-inorganic powders also present some problems in their application, the most prominent of which is their tendency to agglomerate. This is mainly due to the extremely high specific surface area and surface energy of nano-inorganic powders, which cause the particles to attract each other, thus forming agglomerates. Agglomeration of nano-inorganic powders not only reduces their dispersibility and stability but also affects their application in materials such as fibers, leading to problems such as the inability to spin or insufficient strength in the produced fibers.

[0004] To address the agglomeration problem of nano-inorganic powders and improve their dispersibility and stability, extensive research has been conducted, leading to the development of various surface modification methods. Currently, commonly used surface modification methods for nano-inorganic powders include surfactant modification, coupling agent modification, and polymer coating modification. While these methods can improve the properties of nano-inorganic powders to some extent, they also have some drawbacks. For example, surfactant modification is prone to desorption, resulting in unstable modification effects; coupling agent modification is costly and complex, making it difficult to control side reactions during the modification process; the surface properties of the modified nano-inorganic powder are significantly affected by the modification conditions, and the surface modification is not uniform; polymer coating modification may affect the original properties of the nano-inorganic powder. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing surface-hydrophobically modified nano-inorganic powder and functional fibers, which solves the problem of agglomeration caused by the large specific surface area and numerous surface hydroxyl groups of nano-inorganic powder. This solves the problem of uneven dispersion and easy agglomeration of nano-inorganic powder in organic polymers, making the nano-inorganic powder uniformly dispersed in the fibers, thereby improving the comprehensive performance of the composite fibers.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] The first aspect of the present invention provides a method for preparing surface-hydrophobically modified nano-inorganic powders, comprising the following steps:

[0008] S1: React nano-inorganic powder with boric acid by heating to obtain hydroxyl-activated nano-inorganic powder;

[0009] S2: Hydroxyl-activated nano-inorganic powder is reacted with long-chain alkanols to obtain surface-hydrophobically modified nano-inorganic powder.

[0010] Further, in step S1, the nano-inorganic powder is selected from one or more of nano-silica, nano-titanium dioxide, nano-tourmaline, nano-zirconium carbide, or nano-zinc oxide; the particle size of the nano-inorganic powder is 10~500nm, and the mass ratio of the nano-inorganic powder to boric acid is 5~15:1.

[0011] Furthermore, in step S1, the heating reaction is carried out at a temperature of 400-600 °C for 2-5 hours.

[0012] Furthermore, in step S2, the long-chain alkanol has the molecular formula CH3(CH2). n OH, where n=8~14, and the mass ratio of the nano-inorganic powder to the long-chain alkanol is 1:4~8.

[0013] Furthermore, in step S2, the catalyst in the reaction is one or more of concentrated sulfuric acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

[0014] Furthermore, in step S2, the reaction temperature is 70~150 ℃ and the reaction time is 2~7 h.

[0015] A second aspect of the present invention provides a method for preparing functional fibers, comprising: melt-blending and extruding surface-hydrophobic modified nano-inorganic powder, polymer chips, dispersant and antioxidant to obtain functional masterbatch, and melt-spinning to obtain functional fibers;

[0016] The surface-hydrophobic modified nano-inorganic powder was prepared using the method described above.

[0017] Furthermore, the polymer chips are selected from one of polyethylene terephthalate (PET) chips, polyamide chips, and polypropylene chips;

[0018] The dispersant is vinyl bis-stearamide (EBS) or zinc stearate, and its mass content in the functional masterbatch is 0.3-3%.

[0019] The antioxidant is antioxidant 1010 or antioxidant 1076, and its mass content in the functional masterbatch is 0.01~0.5%;

[0020] The surface hydrophobic modified nano-inorganic powder has a mass content of 1-30% in the functional masterbatch.

[0021] Furthermore, the mass content of the surface hydrophobic modified nano-inorganic powder in the functional fiber is 1~10%.

[0022] Furthermore, the melt spinning includes: directly melt spinning the functional masterbatch or mixing it with additionally added polymer chips and then adding it to a melt spinning machine for spinning.

[0023] This invention employs an alcohol ester modification method. The modification principle involves the interaction between the hydroxyl groups of the alkanoic alcohol molecules and the active sites on the surface of the nano-inorganic powder, forming adsorption or chemical bonds. The long-chain hydrocarbon structure constructs a hydrophobic layer on the surface, reducing surface energy. It offers significant advantages: it improves the dispersibility of the nano-inorganic powder, enabling uniform distribution in various media; enhances compatibility with organic matrices, improving fiber quality; the process is simple, easy to operate and control; it is environmentally friendly, with low toxicity and minimal hazard; and it can be adjusted as needed to meet different application requirements.

[0024] Compared with the prior art, the present invention has the following characteristics:

[0025] This invention provides a method for hydrophobic modification of the surface of nano-inorganic powders, its preparation, and its application. First, boric acid is used to activate the reaction sites on the surface of the nano-inorganic powders. Then, long-chain alkanols are used as surface modifiers, and under acid catalysis, the long carbon chains are introduced into the surface of the nano-inorganic powders to prepare modified nano-inorganic powders. This method features a simple processing technology, mild reaction conditions, and does not use toxic organic reagents as solvents. Furthermore, the modifiers can be recycled, making it environmentally friendly and in line with sustainable development. The inorganic powders in the functional masterbatches and functional fibers prepared by melt blending are uniformly dispersed, effectively solving the problems of poor dispersibility and easy agglomeration in organic polymers, thus minimizing the impact on fiber strength and performance. Attached Figure Description

[0026] Figure 1 The image shows the infrared spectra of nano-silica before and after modification in Example 3.

[0027] Figure 2 This is a water contact angle diagram of nano-titanium dioxide before and after modification in Example 7.

[0028] Figure 3 These are scanning electron microscope (SEM) images of the nano-tourmaline powder before and after modification in Example 9. Detailed Implementation

[0029] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0030] The following are more detailed implementation examples, which further illustrate the technical solution of the present invention and the technical effects that can be obtained.

[0031] In the following embodiments, unless otherwise specified, the raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.

[0032] The contact angle testing steps in the following examples are as follows: An appropriate amount of sample powder is placed in a mold and pressed into a pellet under a pressure of 10 MPa. The prepared sample pellet is placed on a glass slide, which is then placed on a sample platform. The platform is adjusted to maintain a horizontal position, the light source is turned on, and the glass slide on the sample platform is positioned in the center of the screen. Deionized water (3 μL) is titrated onto the sample surface using a needle, and a CCD camera is used to record the water droplet morphology in real time to determine the contact angle. Three measurements are performed, and the average contact angle is calculated as the measured sample contact angle.

[0033] The thermal conductivity test method in the following embodiments is as follows: The thermal conductivity of the composite fiber is tested using a TCi type thermal conductivity tester. During the test, the sample is placed on the probe head, and then a 500 g weight is placed on the sample. The test is repeated 5 times and the average value is taken.

[0034] In the following examples, the linear density of the fibers was measured according to the test method of GB / T 14343-2008.

[0035] In the following examples, the breaking strength and breaking elongation of the fibers were measured according to the test method of GB / T 14344-2022.

[0036] In the following examples, the UPF was measured according to the test method of GB / T 18830-2009.

[0037] The negative oxygen ion testing method in the following examples is as follows: The prepared fiber is tested for negative ion performance using an ITC-201A negative ion tester. The fiber is placed about 1 cm away from the tester, and the fiber surface is rubbed with a glass rod at a uniform speed of about 120 times / min.

[0038] In the following examples, the photothermal storage performance was measured according to the test method of GB / T 18319-2019.

[0039] In the following examples, the antibacterial performance was tested according to the GB / T 20944.1-2008 test standard, using the shaking method and evaluated by the plate counting method.

[0040] Example 1

[0041] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0042] (1) Weigh 100 g of 10 nm nano silica powder and 20 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 600 °C for 2 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano silica powder.

[0043] (2) Hydroxyl activated nano silica powder and 3 g p-toluenesulfonic acid were added to 500 g tridecyl alcohol. The nano silica powder was fully dispersed in the tridecyl alcohol by stirring. Then the temperature was raised to 150 °C. After the reaction was carried out for 2 h, the nano silica powder was centrifuged, washed and dried to obtain modified nano silica powder.

[0044] A polyamide 6 functional fiber, the preparation method of which includes the following steps:

[0045] (1) 100 g of modified nano silica powder, 390.5 g of polyamide 6 chips, 7.5 g of EBS and 2 g of antioxidant 1010 were added to a mixer and, after being fully mixed, were transferred to a screw extruder for melt extrusion to obtain polyamide 6 functional masterbatch with silica content of 20%.

[0046] (2) Polyamide 6 functional masterbatch with a silica content of 20% was mixed with polyamide 6 chips and melt-spun to obtain polyamide 6 functional fiber with a silica content of 8%.

[0047] In this embodiment, the contact angle of the unmodified nano-silica sample was measured to be 16°, and the contact angle of the modified nano-silica sample was measured to be 125°. The prepared polyamide 6 / silica functional fiber with a functional powder content of 8% had a linear density of 58 dtex, a tensile strength of 3.4 cN / dtex, an elongation at break of 50%, and a thermal conductivity of 0.0402 W / (m²). K).

[0048] Example 2

[0049] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0050] (1) Weigh 100 g of 40 nm nano silica powder and 15 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 550 °C for 3 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano silica powder.

[0051] (2) Hydroxyl activated nano silica powder and 4 g benzenesulfonic acid were added to 420 g octanol. The nano silica powder was fully dispersed in octanol by stirring. Then the temperature was raised to 110 °C. After the reaction was carried out for 4 h, the nano silica powder was centrifuged, washed and dried to obtain modified nano silica powder.

[0052] A polyamide 6 functional fiber, the preparation method of which includes the following steps:

[0053] (1) 100 g of modified nano silica powder, 889 g of polyamide 6 chips, 10 g of EBS and 1 g of antioxidant 1010 were added to a mixer and after they were fully mixed, they were transferred to a screw extruder for melt extrusion to obtain polyamide 6 functional masterbatch with silica content of 10%.

[0054] (2) Polyamide 6 functional masterbatch with a silica content of 10% was mixed with polyamide 6 chips and melt-spun to obtain polyamide 6 functional fiber with a silica content of 5%.

[0055] In this embodiment, the contact angle of the unmodified nano-silica sample was measured to be 18°, and the contact angle of the modified nano-silica sample was measured to be 117°. The prepared polyamide 6 / silica functional fiber with a functional powder content of 5% had a linear density of 60 dtex, a tensile strength of 4.9 cN / dtex, an elongation at break of 29%, and a thermal conductivity of 0.0447 W / (m²). K).

[0056] Example 3

[0057] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0058] (1) Weigh 300 g of 50 nm nano-silica powder and 25 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 500 °C for 3.5 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano-silica powder.

[0059] (2) Hydroxyl activated nano silica powder and 12 g p-toluenesulfonic acid were added to 1530 g tridecyl alcohol. The nano silica powder was fully dispersed in the tridecyl alcohol by stirring. Then the temperature was raised to 90 °C. After the reaction was carried out for 5 h, the nano silica powder was centrifuged, washed and dried to obtain modified nano silica powder.

[0060] like Figure 1The figure shows the infrared spectra of nano-silica before and after modification in Example 3. In the figure, curve SiO2 represents the nano-silica powder before modification, and curve SiO2Mod represents the infrared spectrum of the nano-silica powder after modification. The horizontal axis represents wavenumber, and the vertical axis represents absorbance. The wavelength range is from 2845 to 2975 cm⁻¹. -1 The absorption peaks of methyl and methylene groups indicate that the grafting modification of the nano-silica surface was successful.

[0061] A polyamide 6 functional fiber, the preparation method of which includes the following steps:

[0062] (1) 300 g of modified nano silica powder, 665 g of polyamide 6 chips, 30 g of EBS and 5 g of antioxidant 1010 were added to a mixer and after they were fully mixed, they were transferred to a screw extruder for melt extrusion to obtain polyamide 6 functional masterbatch with silica content of 30%.

[0063] (2) Polyamide 6 functional masterbatch with a silica content of 30% was mixed with polyamide 6 chips and melt-spun to obtain polyamide 6 functional fiber with a silica content of 10%.

[0064] In this embodiment, the contact angle of the unmodified nano-silica sample was measured to be 16°, and the contact angle of the modified nano-silica sample was measured to be 150°. The prepared polyamide 6 / silica composite fiber with a functional powder content of 10% had a linear density of 60 dtex, a tensile strength of 4.5 cN / dtex, an elongation at break of 30%, and a thermal conductivity of 0.0380 W / (m²). K).

[0065] Example 4

[0066] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0067] (1) Weigh 50 g of 100 nm nano silica powder and 6 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 500 °C for 5 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano silica powder.

[0068] (2) Hydroxyl activated nano silica powder and 2.5 g concentrated sulfuric acid were added to 400 g undecyl alcohol. The nano silica powder was fully dispersed in undecyl alcohol by stirring. Then the temperature was raised to 70 °C. After the reaction was completed for 7 h, the mixture was centrifuged, washed and dried to obtain modified nano silica powder.

[0069] A polyester functional fiber, the preparation method of which includes the following steps:

[0070] (1) Add 50 g of modified nano silica powder, 2440 g of polyester (PET) chips, 7.5 g of zinc stearate and 2.5 g of antioxidant 1076 to a mixer. After they are fully mixed, transfer them to a screw extruder for melt extrusion to obtain polyester chips with a silica content of 2%.

[0071] (2) Polyester functional fibers with a silica content of 2% were obtained by direct melt spinning.

[0072] In this embodiment, the contact angle of the unmodified nano-silica sample was measured to be 21°, and the contact angle of the modified nano-silica sample was measured to be 141°. The obtained polyester / silica functional fiber with a functional powder content of 2% had a linear density of 55 dtex, a breaking strength of 4.0 cN / dtex, a breaking elongation of 32%, and a thermal conductivity of 0.0630 W / (m²). K).

[0073] Example 5

[0074] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0075] (1) Weigh 50 g of 500 nm nano silica powder and 8 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 400 °C for 5 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano silica powder.

[0076] (2) Hydroxyl activated nano silica powder and 1.5 g p-toluenesulfonic acid were added to 200 g octanol. The nano silica powder was fully dispersed in octanol by stirring. Then the temperature was raised to 120 °C. After the reaction was carried out for 2 h, the mixture was centrifuged, washed and dried to obtain modified nano silica powder.

[0077] A polyamide 6 functional fiber, the preparation method of which includes the following steps:

[0078] (1) Add 50 g of modified nano silica powder, 4930 g of polyamide 6 chips, 15 g of EBS and 5 g of antioxidant 1010 to a mixer. After they are fully mixed, transfer them to a screw extruder for melt extrusion to obtain polyamide 6 chips with a silica content of 1%.

[0079] (2) Polyamide 6 functional fibers with a silica content of 1% were obtained by direct melt spinning.

[0080] In this embodiment, the contact angle of the unmodified nano-silica sample was measured to be 25°, and the contact angle of the modified nano-silica sample was measured to be 128°. The prepared polyamide 6 / silica functional fiber with a functional powder content of 1% had a linear density of 57 dtex, a tensile strength of 4.5 cN / dtex, an elongation at break of 58%, and a thermal conductivity of 0.0702 W / (m²). K).

[0081] Example 6

[0082] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0083] (1) Weigh 50 g of 250 nm nano-silica powder and 5 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 550 °C for 2 h. After natural cooling, wash, centrifuge and dry repeatedly with deionized water to obtain hydroxyl-activated nano-silica powder.

[0084] (2) Hydroxyl activated nano silica powder and 1.0 g dodecylbenzene sulfonic acid were added to 200 g tetradecyl alcohol. The nano silica powder was fully dispersed in tetradecyl alcohol by stirring. Then the temperature was raised to 80 °C. After the reaction was carried out for 4 h, the nano silica powder was centrifuged, washed and dried to obtain modified nano silica powder.

[0085] A polypropylene functional fiber, the preparation method of which includes the following steps:

[0086] (1) Add 50 g of modified nano silica powder, 444.5 g of polypropylene chips, 5 g of zinc stearate and 0.5 g of antioxidant 1010 to a mixer. After they are fully mixed, transfer them to a screw extruder for melt extrusion to obtain a polypropylene functional masterbatch with a silica content of 10%.

[0087] (2) Polypropylene functional masterbatch with a silica content of 10% is mixed with polypropylene chips and melt-spun to obtain polypropylene functional fiber with a silica content of 5%.

[0088] In this embodiment, the contact angle of the unmodified nano-silica sample was measured to be 16°, and the contact angle of the modified nano-silica sample was measured to be 119°. The prepared polypropylene / silica functional fiber with a functional powder content of 5% had a linear density of 65 dtex, a tensile strength of 3.5 cN / dtex, an elongation at break of 28%, and a thermal conductivity of 0.0453 W / (m²). K).

[0089] Example 7

[0090] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0091] (1) Weigh 150 g of nano-titanium dioxide powder with a particle size of 50 nm and 10 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 500 °C for 2.5 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano-titanium dioxide powder.

[0092] (2) Hydroxyl activated nano-titanium dioxide powder and 7.5 g p-toluenesulfonic acid were added to 975 g tridecyl alcohol. The nano-titanium dioxide powder was fully dispersed in the tridecyl alcohol by stirring. Then the temperature was raised to 100 °C. After the reaction was carried out for 4 h, the powder was centrifuged, washed and dried to obtain modified nano-titanium dioxide powder.

[0093] A polyester functional fiber, the preparation method of which includes the following steps:

[0094] (1) 150 g of modified nano titanium dioxide powder, 830 g of polyester (PET) chips, 15 g of zinc stearate and 5 g of antioxidant 1076 were added to a mixer and after they were fully mixed, they were transferred to a screw extruder for melt extrusion to obtain a polyester functional masterbatch with a titanium dioxide content of 15%.

[0095] (2) Polyester functional masterbatch with a titanium dioxide content of 15% is mixed with polyester (PET) chips and melt-spun to obtain polyester functional fiber with a titanium dioxide content of 7%.

[0096] In this embodiment, the contact angle of the unmodified nano-titanium dioxide silicon sample was measured to be 14°, and the contact angle of the modified nano-titanium dioxide sample was measured to be 135° (e.g., ...). Figure 2 (As shown). The obtained polyester / titanium dioxide functional fiber with a functional powder content of 7% has a linear density of 62 dtex, a breaking strength of 4.0 cN / dtex, a breaking elongation of 31%, and a UPF value of 478.

[0097] Example 8

[0098] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0099] (1) Weigh 100 g of nano-titanium dioxide powder with a particle size of 25 nm and 13 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 600 °C for 2 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano-titanium dioxide powder.

[0100] (2) Hydroxyl activated nano-titanium dioxide powder and 4 g dodecylbenzenesulfonic acid were added to 500 g octanol. The nano-titanium dioxide powder was fully dispersed in octanol by stirring. Then the temperature was raised to 110 °C. After the reaction was carried out for 5 h, the powder was centrifuged, washed and dried to obtain modified nano-titanium dioxide powder.

[0101] A polyamide 6 functional fiber, the preparation method of which includes the following steps:

[0102] (1) 100 g of modified nano titanium dioxide powder, 1888 g of polyamide 6 chips, 10 g of EBS and 2 g of antioxidant 1010 were added to a mixer and after they were fully mixed, they were transferred to a screw extruder for melt extrusion to obtain polyamide 6 chips with a titanium dioxide content of 5%.

[0103] (2) Polyamide 6 functional fibers with a titanium dioxide content of 5% were obtained by direct melt spinning.

[0104] In this embodiment, the contact angle of the unmodified nano-titanium dioxide sample was measured to be 7°, and the contact angle of the modified nano-titanium dioxide sample was measured to be 120°. The obtained polyamide 6 / titanium dioxide functional fiber with a functional powder content of 5% has a linear density of 50 dtex, a tensile strength of 4.4 cN / dtex, a tensile elongation at break of 40%, and a UPF value of 392.

[0105] Example 9

[0106] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0107] (1) Weigh 60 g of tourmaline nanoparticles with a particle size of 100 nm and 6 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 600 °C for 2 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated tourmaline nanoparticles.

[0108] (2) Hydroxyl activated tourmaline nanoparticles and 2.5 g p-toluenesulfonic acid were added to 375 g tridecyl alcohol. The tourmaline nanoparticles were fully dispersed in the tridecyl alcohol by stirring. The temperature was then raised to 90 °C. After reacting for 2.5 h, the mixture was centrifuged, washed, and dried to obtain modified tourmaline nanoparticles.

[0109] A polyester functional fiber, the preparation method of which includes the following steps:

[0110] (1) 60 g of modified nano tourmaline powder, 532.2 g of polyester (PET) chips, 6 g of zinc stearate and 1.8 g of antioxidant 1076 were added to a mixer and after they were fully mixed, they were transferred to a screw extruder for melt extrusion to obtain a polyester functional masterbatch with a tourmaline content of 10%.

[0111] (2) Polyester functional masterbatch with a tourmaline content of 10% is mixed with polyester (PET) chips and melt-spun to obtain polyester functional fiber with a tourmaline content of 3%.

[0112] like Figure 3 The image shows scanning electron microscope (SEM) images of the nano-tourmaline powder before and after modification in Example 9. In the image, (a) is the unmodified nano-tourmaline powder, and (b) is the SEM image of the modified nano-tourmaline powder. As can be seen from the image, the unmodified nano-inorganic powder is prone to agglomeration, while the surface hydrophobic modification reduces agglomeration and improves dispersibility.

[0113] In this embodiment, the contact angle of the unmodified nano-tourmaline sample was measured to be 15°, and the contact angle of the modified nano-tourmaline sample was measured to be 139°. The obtained polyester / tourmaline functional fiber with a functional powder content of 3% had a linear density of 55 dtex, a breaking strength of 3.3 cN / dtex, a breaking elongation of 30%, and a negative oxygen ion release of 2740 ions / cm³. 3 .

[0114] Example 10

[0115] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0116] (1) Weigh 40 g of zirconium carbide nanoparticles with a particle size of 50 nm and 8 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 550 °C for 4 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated zirconium carbide nanoparticles.

[0117] (2) Hydroxyl activated zirconium carbide nanoparticles and 2 g of p-toluenesulfonic acid were added to 250 g of tridecyl alcohol. The zirconium carbide nanoparticles were fully dispersed in the tridecyl alcohol by stirring. The temperature was then raised to 90 °C. After the reaction was carried out for 3 h, the mixture was centrifuged, washed and dried to obtain modified zirconium carbide nanoparticles.

[0118] A polyester functional fiber, the preparation method of which includes the following steps:

[0119] (1) 40 g of modified nano zirconium carbide powder, 753.6 g of polyester (PET) chips, 4 g of zinc stearate and 2.4 g of antioxidant 1076 were added to a mixer and after they were fully mixed, they were transferred to a screw extruder for melt extrusion to obtain polyester functional masterbatch with zirconium carbide content of 5%.

[0120] (2) Polyester functional masterbatch with zirconium carbide content of 5% is mixed with polyester (PET) chips and melt-spun to obtain polyester functional fiber with zirconium carbide content of 1.5%.

[0121] In this embodiment, the contact angle of the unmodified nano-zirconium carbide sample was measured to be 33°, and the contact angle of the modified nano-zirconium carbide sample was measured to be 130°. The obtained polyester / zirconium carbide functional fiber with a functional powder content of 1.5% has a linear density of 50 dtex, a breaking strength of 3.5 cN / dtex, a breaking elongation of 30%, and a maximum temperature rise of 7.5 ℃ for photothermal storage performance.

[0122] Example 11

[0123] A surface-hydrophobically modified nano-inorganic powder, the preparation method of which includes the following steps:

[0124] (1) Weigh 50 g of 40 nm nano zinc oxide powder and 5 g of boric acid into a clean crucible, mix them evenly, and then place them in a high-temperature furnace and react at 400 °C for 5 h. After natural cooling, wash repeatedly with deionized water, centrifuge, and dry to obtain hydroxyl-activated nano zinc oxide powder.

[0125] (2) Hydroxyl activated nano zinc oxide powder and 1.4 g p-toluenesulfonic acid were added to 250 g undecyl alcohol. The nano zinc oxide powder was fully dispersed in undecyl alcohol by stirring. Then the temperature was raised to 140 °C. After the reaction was carried out for 3 h, the mixture was centrifuged, washed and dried to obtain modified nano zinc oxide powder.

[0126] A polyester functional fiber, the preparation method of which includes the following steps:

[0127] (1) Add 50 g of modified nano zinc oxide powder, 442.5 g of polyester (PET) chips, 5 g of zinc stearate and 2.5 g of antioxidant 1076 to a mixer. After they are fully mixed, transfer them to a screw extruder for melt extrusion to obtain a polyester functional masterbatch with a zinc oxide content of 10%.

[0128] (2) Polyester functional masterbatch with zinc oxide content of 10% is mixed with polyester (PET) chips and melt-spun to obtain polyester functional fiber with zinc oxide content of 5%.

[0129] In this embodiment, the contact angle of the unmodified nano-zinc oxide sample was measured to be 20°, and the contact angle of the modified nano-zinc oxide sample was measured to be 124°. The obtained polyester / zinc oxide functional fiber with a functional powder content of 5% has a linear density of 48 dtex, a breaking strength of 3.2 cN / dtex, a breaking elongation of 27%, and an antibacterial rate of more than 99% against Staphylococcus aureus and Escherichia coli.

[0130] The method for preparing modified nano-inorganic powders in this invention is simple, the reaction conditions are mild, no toxic organic reagents are used as solvents, and the modifier can be recycled. The modified nano-inorganic powders obtained have good hydrophobicity, and the inorganic powders in the prepared functional masterbatches and functional fibers are uniformly dispersed, which can effectively solve the problems of poor dispersibility and easy agglomeration in organic polymers.

[0131] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing surface-hydrophobically modified nano-inorganic powder, characterized in that, Includes the following steps: S1: The nano-inorganic powder is heated and reacted with boric acid at 400~600 ℃ for 2~5 h to obtain hydroxyl-activated nano-inorganic powder; the nano-inorganic powder is selected from one or more of nano-silica, nano-titanium dioxide, nano-tourmaline, nano-zirconium carbide or nano-zinc oxide; the particle size of the nano-inorganic powder is 10~500 nm, and the mass ratio of the nano-inorganic powder to boric acid is 5~15:1; S2: Hydroxyl-activated nano-inorganic powder is reacted with long-chain alkanols to obtain surface-hydrophobically modified nano-inorganic powders; the molecular formula of the long-chain alkanols is CH3(CH2). n OH, where n=8~14, and the mass ratio of the nano-inorganic powder to the long-chain alkanol is 1:4~8.

2. The method for preparing surface-hydrophobically modified nano-inorganic powder according to claim 1, characterized in that, In step S2, the catalyst in the reaction is one or more of concentrated sulfuric acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

3. The method for preparing surface-hydrophobically modified nano-inorganic powders according to claim 1, characterized in that, In step S2, the reaction temperature is 70~150 ℃ and the reaction time is 2~7 h.

4. A method for preparing a functional fiber, characterized in that, include: Functional masterbatch is prepared by melt-blending and extruding surface-hydrophobic modified nano-inorganic powder, polymer chips, dispersant and antioxidant, and then melt-spinning to obtain functional fibers. The surface-hydrophobic modified nano-inorganic powder is prepared by the method described in any one of claims 1 to 3.

5. The method for preparing functional fibers according to claim 4, characterized in that, The polymer chips are selected from one of polyethylene terephthalate chips, polyamide chips, and polypropylene chips. The dispersant is vinyl bis-stearamide or zinc stearate, and its mass content in the functional masterbatch is 0.3-3%. The antioxidant is antioxidant 1010 or antioxidant 1076, and its mass content in the functional masterbatch is 0.01~0.5%; The surface hydrophobic modified nano-inorganic powder has a mass content of 1-30% in the functional masterbatch.

6. The method for preparing functional fibers according to claim 4, characterized in that, The surface hydrophobic modified nano-inorganic powder has a mass content of 1~10% in the functional fiber.

7. The method for preparing functional fibers according to claim 4, characterized in that, The melt spinning process includes: directly melt spinning the functional masterbatch or mixing it with additionally added polymer chips and then adding it to a melt spinning machine for spinning.

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