Tourmaline-ge oxide-titania composite nanomaterial, and preparation method and application thereof

Abstract

The application discloses a tourmaline germanium oxide titanium dioxide composite nanomaterial and a preparation method and application thereof. The composite nanomaterial is prepared by using a brand-new negative ion releasing mechanism, and is used for preparing a new negative ion releasing fiber. The nanometer powder prepared by the application can play a catalytic polymerization role in in-situ polymerization, and does not need to use an additional catalyst. The tourmaline serves as a dispersion carrier of the germanium oxide and titanium dioxide nanometer powder, can control the polymerization reaction speed, improve the reaction uniformity, makes the polyamide 6 molecular weight more uniform, and is favorable to improving the spinnability and fiber mechanical property of the spinning fiber.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of functional textile materials, and particularly relates to a tourmaline-germanium oxide-titanium dioxide composite nanomaterial and a preparation method and application thereof. BACKGROUND

[0002] With the improvement of people's living standards, more and more attention is paid to the environment, especially air quality. Negative ions can settle PM2.5, decompose pollutants such as formaldehyde in the air, and have the function of purifying air. In the field of functional textiles, negative ion textiles are also an important member, but the problem of negative ion release has always been an important topic in the development of functionalization of chemical fiber fabrics. At present, there are some solutions, such as solving the problem from the source of the fiber. Negative ion release fibers can be prepared, such as using high addition amount and composite spinning technology to prepare negative ion release fibers. The negative ion release powder used is rare earth, tourmaline, germanium oxide, etc.

[0003] However, the current such fibers also have irreparable defects: first, the use of rare earth and tourmaline powder has the risk of radiation and has safety hazards; second, the negative ion release amount of pure tourmaline or tourmaline-titanium dioxide composite system is limited; third, metal salt series are also used to prepare negative ion release functional fibers, such as using thorium nitrate as a negative ion release agent, but in the later dyeing and finishing, metal ions are precipitated due to the high temperature and high pressure water, which leads to the decline of negative ion release effect and affects the washability of the fabric negative ion release function, so the application is also limited.

[0004] At present, the more common fabric on the market is to realize the negative ion release function of the fabric by using negative ion release finishing. This method has lower cost and remarkable effect compared with the use of negative ion release fibers, so it is also used by most fabric manufacturers. However, this method, although low-cost and effective, also has unavoidable defects: (1) additional pollution. At present, negative ion release finishing is generally used, which increases the pollution degree of wastewater and increases the difficulty of wastewater treatment; (2) insufficient durability. The negative ion release finishing method used at present has poor washability, and few can meet the standard requirements of washability. SUMMARY

[0005] This section aims to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of the specification to avoid obscuring the purpose of this section, abstract and title, and such simplifications or omissions cannot be used to limit the scope of the present application.

[0006] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0007] Therefore, the present application aims at overcoming the deficiencies in the prior art and providing a tourmaline germanium oxide titanium dioxide composite nanomaterial.

[0008] To solve the above technical problems, the present application provides the following technical solutions: the composite nanomaterial is composed of a powder having a negative ion releasing function and sodium hexametaphosphate;

[0009] The powder includes, in terms of mass percentage, 75-93% tourmaline, 5-15% nanometer titanium dioxide, and 2-10% germanium oxide.

[0010] The addition amount of the sodium hexametaphosphate is 0.1-1% of the powder having the negative ion releasing function.

[0011] Another purpose of the present application is to provide a preparation method of the tourmaline germanium oxide titanium dioxide composite nanomaterial, comprising,

[0012] Sodium hexametaphosphate is added to the powder having the negative ion releasing function, and after being stirred uniformly, water is added to perform grinding through a liquid phase grinding device to obtain a negative ion releasing function nanometer powder water blend.

[0013] The powder water blend is subjected to a polymerization reaction in a hydration kettle, and after the reaction, concentration is performed to obtain a negative ion releasing function nanometer powder water blend, which is the tourmaline germanium oxide titanium dioxide composite nanomaterial.

[0014] As a preferred scheme of the preparation method of the tourmaline germanium oxide titanium dioxide composite nanomaterial, in the liquid phase grinding process, the powder concentration is 5-30%.

[0015] As a preferred scheme of the preparation method of the tourmaline germanium oxide titanium dioxide composite nanomaterial, in the liquid phase grinding process, the grinding time is 2-6h, and the powder particle size is 80-120nm.

[0016] As a preferred scheme of the preparation method of the tourmaline germanium oxide titanium dioxide composite nanomaterial, in the polymerization reaction, the reaction temperature is 60-120℃, and the reaction time is 3-6h.

[0017] As a preferred scheme of the preparation method of the tourmaline germanium oxide titanium dioxide composite nanomaterial, the concentration is concentrated to a solid content of the negative ion releasing function nanometer powder water blend of 40-50%.

[0018] Another purpose of the present application is to provide an application of the tourmaline germanium oxide titanium dioxide composite nanomaterial in preparing fibers having a negative ion releasing function, comprising,

[0019] The tourmaline germanium oxide titanium dioxide composite nanomaterial is blended with caprolactam, water is added as a ring-opening agent, and through ring-opening prepolymerization, post-polycondensation, boiling water extraction and drying, the polyamide 6 chip with the negative ion release function is obtained.

[0020] After the polyamide 6 chip is dried, it is fed into a feeder of a spinning machine for melt spinning, so that the fiber with the negative ion release function is obtained.

[0021] As a preferred scheme of the application of the tourmaline germanium oxide titanium dioxide composite nanomaterial, the addition amount of the tourmaline germanium oxide titanium dioxide composite nanomaterial is 0.5-6% compared with caprolactam.

[0022] As a preferred scheme of the application of the tourmaline germanium oxide titanium dioxide composite nanomaterial, the single filament fineness of the fiber with the negative ion release function is set to 0.5-5D.

[0023] The application has the following beneficial effects:

[0024] The application adopts a new negative ion release mechanism to prepare a new negative ion release fiber, the tourmaline and germanium oxide release negative ion functions are compounded, and the nanometer powder prepared by the application technology can play a catalytic polymerization role in in-situ polymerization, without the need of using an additional catalyst, the tourmaline serves as a dispersion carrier of the germanium oxide and titanium dioxide nanometer powder, can control the polymerization reaction speed, improve the reaction uniformity, makes the polyamide 6 molecular weight more uniform, and is beneficial to improving the spinnability and fiber mechanical properties of the spinning fiber. DETAILED DESCRIPTION

[0025] In order to make the above-mentioned purposes, features and advantages of the application more obvious and easy to understand, the specific implementation manner of the application will be described in detail below with reference to the embodiments of the specification.

[0026] In the following description, many specific details are set forth in order to provide a thorough understanding of the application, but the application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the connotation of the application, therefore the application is not limited by the specific embodiments disclosed below.

[0027] Secondly, the "one embodiment" or "embodiment" referred to herein means that a specific feature, structure or property can be included in at least one implementation manner of the application. "In one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is it an independent or alternative embodiment that excludes other embodiments.

[0028] The raw materials used in the application are commercially available in the art without special instructions.

[0029] The application tests the particle size of the material by a laser particle size analyzer, and tests the negative ion release effect of the material according to the test standard of GB / T 30128-2013.

[0030] Example 1

[0031] The embodiment provides a preparation method of tourmaline germanium oxide titanium dioxide composite nanomaterial and application of the material in a spun fiber, and specifically relates to the following:

[0032] 1) The powder with a negative ion release function is compounded according to the following mass percentages:

[0033] 85% of tourmaline, 10% of nanometer titanium dioxide, and 5% of germanium oxide;

[0034] 2) 0.5% of sodium hexametaphosphate is added to the powder, the powder is uniformly stirred, and then is grinded through a liquid phase grinding device, a grinding time is 4h, a grinding medium is water, and a powder concentration is 20%, so that a negative ion release function nanometer powder water blend is obtained;

[0035] 3) The powder water blend is reacted in a hydration kettle, reacts at 100 DEG C for 4h, is concentrated to a negative ion release function nanometer powder water blend with a concentration of 50%, and a concentrated slurry is obtained.

[0036] 4) The concentrated slurry is blended with caprolactam according to 4% of the mass fraction of the resin, and 1% of water is added as a ring-opening agent, pre-polymerization is carried out at a ring-opening temperature of 170 DEG C for 65min; post-polycondensation is carried out at a temperature of 260 DEG C for 4.5h; boiling water extraction is carried out for 24h, a bath ratio is 1:1; drying is carried out at a temperature of 110 DEG C for 6h, and a negative ion release function polyamide 6 chip is obtained.

[0037] 5) After the negative ion release function polyamide 6 chip is dried, the chip is fed into a feeder of a spinning machine to carry out melt spinning, a spinning temperature is 270 DEG C, a spinning speed is 2600m / min, an initial pressure of a spinning assembly is 12MPa, a spinning fiber diameter is set to 1D, the remaining process steps are the same as those of example 1, and a negative ion release polyamide 6 fiber of the embodiment is obtained.

[0038] Example 2

[0039] The embodiment is different from example 1 in that the spinning fiber diameter in step 5) is set to 3D, and the remaining process steps are the same as those of example 1, and a negative ion release polyamide 6 fiber of the embodiment is obtained.

[0040] Comparative example 1

[0041] The difference between this embodiment and example 1 is that the diameter of the spinning fiber in step 5) is set to 0.5D, and the remaining process steps are the same as example 1, to obtain the negative ion releasing polyamide 6 fiber of the present comparative example.

[0042] Comparative example 3

[0043] The difference between this embodiment and example 1 is that the diameter of the spinning fiber in step 5) is set to 5D, and the remaining process steps are the same as example 1, to obtain the negative ion releasing polyamide 6 fiber of the present comparative example.

[0044] The negative ion releasing effect of the negative ion releasing polyamide 6 fiber of the above examples and comparative examples is determined, and the results are shown in Table 1.

[0045] Table 1

[0046]

[0047] As can be seen from Table 1, reducing the fiber diameter can increase the specific surface area of the fiber, at this time the distribution amount of the negative ion releasing powder on the surface increases, and the negative ion release amount increases. When the fiber diameter is further reduced in example 2, the promotion effect of the negative ion release amount becomes slow, and at this time the fiber spinning performance is poor, the fiber strength is not enough, and the brittleness is large, so it is suitable for spinning fibers with a single fiber diameter ≥1D.

[0048] Example 3

[0049] The difference between this embodiment and example 1 is that the functional powder formula in step 1) is adjusted, specifically:

[0050] 1) The powder with negative ion releasing function is compounded according to the following mass percentage:

[0051] 93% of tourmaline, 5% of nano titanium dioxide, and 2% of germanium oxide;

[0052] The remaining process steps are the same as example 1, to obtain the negative ion releasing polyamide 6 fiber of the present embodiment.

[0053] Example 4

[0054] The difference between this embodiment and example 1 is that the functional powder formula in step 1) and the grinding time in step 2) are adjusted, specifically:

[0055] 1) The powder with negative ion releasing function is compounded according to the following mass percentage:

[0056] 75% of tourmaline, 15% of nano titanium dioxide, and 10% of germanium oxide;

[0057] 2) 0.5% of sodium hexametaphosphate is added to the powder, which is stirred uniformly and then grinded by a liquid-phase grinding device, the grinding time is 6h, the grinding medium is water, and the powder concentration is 20%, to obtain a nano-powder water blend with anion-releasing function;

[0058] The remaining process steps are the same as those in Example 1, and the anion-releasing polyamide 6 fiber of this example is obtained.

[0059] The particle size of the anion-releasing functional powder and the anion-releasing effect of the polyamide 6 fiber of Examples 1 and 3 and 4 are determined, and the results are shown in Table 2.

[0060] Table 2

[0061]

[0062] As can be seen from Table 2, within a certain range, increasing the addition amount of titanium dioxide and germanium dioxide can improve the release effect of negative ions, but when the content of titanium dioxide and germanium dioxide is too high (Example 4), although the release effect of negative ions increases, the growth rate slows down, and the fiber becomes yellow and brittle at this time, which is due to the excessive content of titanium dioxide and germanium dioxide as catalysts, leading to uneven polymerization. At this time, increasing the grinding time does not reduce the particle size, indicating that the grinding limit has been reached.

[0063] Example 5

[0064] This example is used to explore the effect of powder concentration during grinding on the performance of the functional powder and fiber. Unlike Example 1, the powder concentration in step 2) is adjusted to 5%, 10%, 15%, 20%, and 25%, respectively, and the remaining process steps are the same as those in Example 1, to obtain the anion-releasing functional powder and polyamide 6 fiber under different powder concentrations in this example.

[0065] The particle size of the anion-releasing functional powder and the anion-releasing effect of the polyamide 6 fiber of this example are determined, and the results are shown in Table 3.

[0066] Table 3

[0067]

[0068] As can be seen from Table 3, the powder concentration during grinding has a significant effect on the particle size of the powder and the release amount of negative ions. Within a certain range, increasing the grinding concentration of the powder can reduce the particle size and increase the release amount of negative ions, but further increasing the grinding concentration will decrease the grinding effect, so 20% is the best grinding concentration.

[0069] Example 6

[0070] This example is to explore the effect of hydration reaction temperature on the performance of the functional powder and fiber, which is different from example 1. The hydration reaction temperature in step 3) is adjusted to 60℃, 80℃, 100℃, 120℃ respectively, and the rest of the process steps are the same as example 1. The negative ion release functional powder and polyamide 6 fiber under different hydration reaction temperatures are obtained.

[0071] The particle size of the negative ion release functional powder and the negative ion release effect of the polyamide 6 fiber are measured, and the results are shown in Table 4.

[0072] Table 4

[0073]

[0074]

[0075] From Table 4, it can be seen that within a certain range, by increasing the hydration kettle reaction temperature, the negative ion release amount is greatly improved, which shows that there is a chemical synergistic effect between germanium dioxide and titanium dioxide and tourmaline, not just a simple physical compounding. However, the negative ion release amount cannot be further improved by continuing to increase the hydration kettle reaction temperature.

[0076] Example 7

[0077] This example is to explore the effect of the doping amount of functional powder in the fiber on the performance of the fiber, which is different from example 1. The concentrated slurry addition amount in step 4) is adjusted to 1%, 2%, 4%, 6% respectively, and the rest of the process steps are the same as example 1. The negative ion release functional powder polyamide 6 fiber with different concentrated slurry addition amounts is obtained.

[0078] The negative ion release effect of the negative ion release functional polyamide 6 fiber is measured, and the results are shown in Table 5.

[0079] Table 5

[0080]

[0081] From Table 5, it can be seen that by increasing the content of negative ion functional powder, the release amount of negative ions can be increased, but when the addition amount is 6%, there is no significant improvement compared to 4%, and at this time the spinning performance decreases, and the broken and floating silk phenomenon occurs. Therefore, the content of negative ion functional powder is set to 4%.

[0082] In conclusion, the application adopts a brand-new negative ion releasing mechanism to prepare a new negative ion releasing fiber, the fiber can be made into white / light color, has permanent negative ion releasing function, the mechanical property can reach the standard of common fiber, completely meets the requirements of various weaving, the cost is equivalent to the negative ion releasing finishing, and the nanometer powder prepared by the application can play a catalytic polymerization role in in-situ polymerization, without additional use of catalyst, compared with the currently used negative ion releasing fiber, the cost is reduced by 60-80%, pollution is reduced, the titanium dioxide and germanium oxide take the tourmaline as a dispersion carrier, the polymerization degree can be effectively controlled, and the performance of the polyamide 6 is improved.

[0083] It should be noted that the above examples are only used to illustrate the technical solutions of the application and are not limiting. Although the application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the application can be modified or replaced equivalently without departing from the spirit and scope of the technical solutions of the application, which should be covered in the scope of the claims of the application.

Claims

1. The application of a tourmaline-germanium oxide-titanium dioxide composite nanomaterial in the preparation of fibers with negative ion release function, characterized in that: The composite nanomaterial is composed of powder with negative ion release function and sodium hexametaphosphate. By mass percentage, the powder includes 85-93% tourmaline, 5-10% nano titanium dioxide, and 2-5% germanium oxide. The amount of sodium hexametaphosphate added is 0.1-1% of the powder with negative ion release function. The preparation method of the tourmaline-germanium oxide-titanium dioxide composite nanomaterial is as follows: Sodium hexametaphosphate was added to the powder with negative ion release function, stirred evenly, and then water was added and liquid-phase grinding was carried out through a liquid-phase grinding device to obtain a water blend of nano-powder with negative ion release function. The powder water blend is then polymerized in a hydration reactor at a temperature of 60-120℃ for 3-6 hours. After the reaction, it is concentrated to obtain a negative ion releasing nano-powder water blend, which is a tourmaline germanium oxide titanium dioxide composite nanomaterial. The concentration is described as a concentration of 50% in a water-based blend of nanoparticles with negative ion-releasing function. The tourmaline-germanium oxide-titanium dioxide composite nanomaterial is used to prepare fibers with negative ion release function. The method for preparing the fibers is as follows: Tourmaline germanium oxide titanium dioxide composite nanomaterials were blended with caprolactam, wherein the amount of tourmaline germanium oxide titanium dioxide composite nanomaterials added was 4% compared to caprolactam; Water was added as a ring-opening agent, and the mixture was subjected to ring-opening prepolymerization, post-condensation polymerization, boiling water extraction, and drying to obtain polyamide 6 chips with negative ion release function. After the polyamide 6 chips are dried, they are fed into the feeder of a spinning machine for melt spinning, thus obtaining fibers with negative ion release function.

2. The application of the tourmaline-germanium oxide-titanium dioxide composite nanomaterial as described in claim 1 in the preparation of fibers with negative ion release function, characterized in that: The powder concentration in the liquid phase grinding process is 5-30%.

3. The application of the tourmaline-germanium oxide-titanium dioxide composite nanomaterial as described in claim 1 in the preparation of fibers with negative ion release function, characterized in that: The liquid phase grinding time is 2-6 hours, and the powder is ground until the particle size is 80-120 nm.

4. The application of the tourmaline-germanium oxide-titanium dioxide composite nanomaterial as described in claim 1 in the preparation of fibers with negative ion release function, characterized in that: The single filament fineness of the fiber with negative ion release function is set to 0.5-5D.

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