Sun-protecting polyester based on monoatomic anti-ultraviolet filler and preparation method thereof

Abstract

The present application relates to the field of textile materials, and more particularly to a sunscreen polyester and a preparation method thereof, which comprises the following steps: S1: preparing an iron monatomic / hydrotalcite sunscreen filler by hydrothermal reaction under alkaline conditions, using an iron source, a divalent metal salt and a trivalent metal salt as raw materials; S2: grinding the iron monatomic / hydrotalcite sunscreen filler to obtain a filler powder; and S3: mixing the filler powder with a PET master batch, melting, and preparing the sunscreen polyester by solution mixing spinning. The preparation method of the sunscreen polyester provided by the present application introduces the self-prepared iron monatomic / hydrotalcite sunscreen filler, improves the ultraviolet resistance of the polyester, endows the polyester with long-acting and wash-resistant sunscreen effect, and improves the durability of the ultraviolet resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of textile materials, and particularly relates to a sunscreen polyester and a preparation method thereof. BACKGROUND

[0002] With the improvement of people's living standards and the enhancement of health consciousness, fiber products with sunscreen function are increasingly widely used in outdoor clothing, sports equipment, automotive interiors and other fields. Polyester becomes an important base material for preparing sunscreen functional fibers due to its excellent physical properties and processing performance. However, the resistance of polyester to ultraviolet rays is limited, and long-term exposure to ultraviolet rays can cause aging, resulting in problems such as fiber strength reduction and color fading.

[0003] In order to improve the anti-ultraviolet performance of polyester, the commonly used methods currently include adding ultraviolet absorbers, reflectants and the like. However, the traditional ultraviolet absorbers often have poor weather resistance and are prone to migration, which leads to poor durability of the anti-ultraviolet performance of polyester and affects the long-term use effect of polyester. Therefore, developing a polyester with durable anti-ultraviolet performance is of great significance for improving the sunscreen function of polyester. SUMMARY

[0004] In order to solve the problem of poor durability of the anti-ultraviolet performance of polyester in the prior art, the present application provides a preparation method of sunscreen polyester, which introduces iron monatomic / hydrotalcite sunscreen filler into polyester through the way of original liquid mixing, so that the filler is firmly combined with polyester and uniformly dispersed, thereby improving the sunscreen performance of polyester and the durability of its anti-ultraviolet performance, and solving the problem of poor durability of the anti-ultraviolet performance of polyester in the prior art.

[0005] The technical scheme adopted by the present application to solve its technical problems is:

[0006] A preparation method of sunscreen polyester, comprising the following steps:

[0007] S1: preparing iron monatomic / hydrotalcite sunscreen filler by hydrothermal reaction under alkaline conditions, using iron source, divalent metal salt and trivalent metal salt as raw materials;

[0008] S2: grinding the iron monatomic / hydrotalcite sunscreen filler to obtain filler powder;

[0009] S3: mixing the filler powder with PET masterbatch, melting, and preparing sunscreen polyester by original liquid mixing spinning.

[0010] Optionally, the pH of the alkaline condition is 9-12.

[0011] Optionally, the temperature range of the hydrothermal reaction is 100-200℃.

[0012] Optionally, the molar ratio of the iron source, the divalent metal salt and the trivalent metal salt in step S1 is 1:2:6.

[0013] Optionally, the iron source is selected from at least one of ferric nitrate, ferric sulfate and ferric chloride.

[0014] Optionally, the divalent metal salt is selected from at least one of magnesium nitrate, magnesium sulfate and magnesium chloride.

[0015] Optionally, the trivalent metal salt is selected from at least one of aluminum nitrate, aluminum sulfate and aluminum chloride.

[0016] Optionally, the particle size of the filler powder in step S2 is 50-100 nm.

[0017] Optionally, the mass ratio of the filler powder to the PET master batch in step S3 is 1:(30-50).

[0018] Another object of the present application is to provide a sunscreen polyester prepared by the preparation method of the sunscreen polyester as described above.

[0019] The present application has the following beneficial effects:

[0020] The preparation method of the sunscreen polyester provided by the present application introduces the self-prepared iron monatomic / hydrotalcite sunscreen filler, improves the anti-ultraviolet performance of the polyester, endows the polyester with long-acting and wash-resistant sunscreen effect, and improves the durability of the anti-ultraviolet performance. BRIEF DESCRIPTION OF DRAWINGS

[0021] The present application is further described below in combination with the drawings and examples.

[0022] Figure 1 Fig. 1 is a SEM image of the iron monatomic / hydrotalcite sunscreen filler prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0023] The present application is now described in further detail. The examples described below are exemplary and are intended to serve to explain the present application, and cannot be understood as limiting the present application. Based on the examples of the present application, all other examples obtained by those skilled in the art without making creative efforts are within the scope of protection of the present application.

[0024] To solve the problem of poor durability of the anti-ultraviolet performance of the polyester in the prior art, the present application provides a preparation method of a sunscreen polyester, which comprises the following steps:

[0025] S1: preparing an iron monatomic / hydrotalcite sunscreen filler by hydrothermal reaction under alkaline conditions, using an iron source, a divalent metal salt and a trivalent metal salt as raw materials;

[0026] In this step, the divalent metal salt and the trivalent metal salt are reacted by hydrothermal reaction under alkaline conditions to generate hydrotalcite; at the same time, the iron source is simultaneously reacted to enter the trivalent metal position to generate iron atoms; since the iron atoms are generated in situ during the generation of the hydrotalcite, the generated iron atoms are embedded in the hydrotalcite layer in the form of single atoms to form the iron single atom / hydrotalcite sunscreen filler.

[0027] The hydrotalcite has good ultraviolet shielding performance and chemical stability as a layered double hydroxide, and can also have certain anti-ultraviolet performance when used alone for polyester.

[0028] Specifically, the hydrotalcite layer shields UVB through quantum size effect; the iron single atom has a unique electronic structure and can enhance light absorption capacity, but is easy to agglomerate and lose effectiveness when used alone; the iron single atom / hydrotalcite composite structure constructed by the application helps to realize uniform dispersion of the iron atoms, which can not only improve the anti-ultraviolet aging performance, but also endow the polyester with long-acting and wash-resistant sunscreen effect and improve the durability of the anti-ultraviolet performance.

[0029] The application constructs an atomic-level dispersion structure by one-step hydrothermal method, avoids the complexity of multiple loadings in the traditional impregnation method, and has excellent structural stability.

[0030] S2: grinding the iron single atom / hydrotalcite sunscreen filler to obtain filler powder;

[0031] S3: mixing the filler powder with PET masterbatch, melting, and preparing sunscreen polyester through dope mixing spinning.

[0032] Since the sunscreen filler is introduced into the polyester by the method of mixing, melting and dope mixing spinning, the filler is uniformly dispersed in the polyester, the bonding force between the filler and the polyester is improved, and the durability of the anti-ultraviolet performance is further improved.

[0033] The preparation method of the sunscreen polyester provided by the application introduces the self-prepared iron single atom / hydrotalcite sunscreen filler to improve the anti-ultraviolet performance of the polyester, endow the polyester with long-acting and wash-resistant sunscreen effect, and improve the durability of the anti-ultraviolet performance.

[0034] To ensure the smooth progress of the hydrothermal reaction, the pH of the alkaline condition in step S1 is preferably 9-12, the temperature range of the hydrothermal reaction is preferably 100-200 DEG C, the molar ratio of the iron source, the divalent metal salt and the trivalent metal salt in step S1 is preferably 1:2:6.

[0035] Further, the iron source is preferably ferric nitrate; the divalent metal salt is preferably magnesium nitrate; and the trivalent metal salt is preferably aluminum nitrate.

[0036] In order to improve the uniformity of the filler mixed with PET, the particle size of the filler powder in step S2 is preferably 50-100 nm.

[0037] In order to take into account the sunscreen performance and mechanical performance, the mass ratio of the filler powder to the PET master batch in step S3 is preferably 1:(30-50).

[0038] It should be noted that, in the preparation process of the sunscreen polyester provided by the present application, corresponding auxiliaries can also be added as needed.

[0039] The sunscreen filler of iron monatomic / hydrotalcite prepared in the present application has excellent anti-ultraviolet performance, can significantly improve the ultraviolet absorption performance of the material, the filler is firmly combined with the polyester and uniformly distributed, and can significantly improve the sunscreen performance of the fiber, and the modified polyester maintains good processing performance and wearing performance, and is suitable for various textile processing processes.

[0040] Another object of the present application is to provide a sunscreen polyester prepared by the preparation method of the sunscreen polyester as described above.

[0041] The sunscreen polyester provided by the present application introduces the self-prepared sunscreen filler of iron monatomic / hydrotalcite through the way of dope mixing spinning in the preparation process, improves the anti-ultraviolet performance of the polyester, and at the same time, gives the polyester long-acting and wash-resistant sunscreen effect, and improves the durability of the anti-ultraviolet performance.

[0042] In order to make the above-mentioned objects, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the drawings.

[0043] Example 1

[0044] The present embodiment provides a preparation method of a sunscreen polyester, which comprises the following steps:

[0045] S1: iron nitrate, aluminum nitrate and magnesium nitrate are mixed in a molar ratio of 1:2:6, added into deionized water, and a lye (sodium hydroxide solution) is added to adjust the pH value of the solution to 9, and stirred for 1 hour to obtain an iron-containing hydrotalcite precursor solution; the precursor solution is transferred to a reaction kettle, and hydrothermal treatment is carried out at 120 DEG C for 24 hours, so that the iron atoms are embedded in the interlayer of the hydrotalcite in the form of monatomic, and a sunscreen filler of iron monatomic / hydrotalcite is obtained;

[0046] S2: after the sunscreen filler of iron monatomic / hydrotalcite is washed, it is dried at 80 DEG C for 12 hours, and ground to obtain a filler powder with a particle size of 50-100 nm, as shown in FIG. 1; Figure 1

[0047] ​S3: The filler powder and the PET master batch are mixed according to a mass ratio of 1:49, a film is prepared by melt mixing and spinning, and is dried at 80℃ for 2 hours to prepare the sunscreen polyester; wherein the process parameters of the melt mixing and spinning are as follows: the spinning temperature is set to 245 o C, the screw rotation speed is set to 10 r / min, and the winding speed of the roller is 600 m / min.

[0048] Example 2

[0049] The difference between this example and Example 1 is that the filler powder and the PET master batch are mixed according to a mass ratio of 1:45 in step S2.

[0050] Example 3

[0051] The difference between this example and Example 1 is that the filler powder and the PET master batch are mixed according to a mass ratio of 1:50 in step S2.

[0052] Example 4

[0053] The difference between this example and Example 1 is that the hydrothermal reaction temperature in step S1 is 150℃.

[0054] Example 5

[0055] The difference between this example and Example 1 is that the hydrothermal reaction temperature in step S1 is 180℃.

[0056] The various comparative examples in the present application are used for comparison with Example 1.

[0057] Comparative Example 1

[0058] The present comparative example provides a preparation method of polyester, which comprises the following process: the PET master batch is prepared into a film by melt mixing and spinning, and is dried at 80℃ for 2 hours.

[0059] Comparative Example 2

[0060] The present comparative example provides a preparation method of sunscreen polyester, which comprises the following steps:

[0061] S1: Aluminum nitrate and magnesium nitrate are mixed according to a molar ratio of 1:2, deionized water is added, sodium hydroxide solution is added to adjust the pH value of the solution to 9, and stirring is carried out for 1 hour to obtain a hydrotalcite precursor solution; the precursor solution is transferred to a reaction kettle, and is subjected to hydrothermal treatment at 120℃ for 24 hours to obtain a hydrotalcite sunscreen filler;

[0062] S2: After the hydrotalcite composite sunscreen filler is washed, it is dried at 80℃ for 12h, and is ground to obtain a filler powder with a particle size of 50-100nm;

[0063] S3: The filler powder and the PET master batch are mixed according to a mass ratio of 1:49, a film is prepared by melt mixing and spinning, and is dried at 80°C for 2 hours to prepare the sunscreen polyester; wherein the process parameters of melt mixing and spinning are as follows: the spinning temperature is set to 245 o C, the screw rotation speed is set to 10 r / min, and the winding speed of the drum is 600 m / min.

[0064] Comparative Example 3

[0065] The present comparative example provides a preparation method of sunscreen polyester, which comprises the following steps:

[0066] S1: Aluminum nitrate and magnesium nitrate are mixed according to a molar ratio of 1:3, deionized water is added, a sodium hydroxide solution is added to adjust the pH value of the solution to 9, and stirring is carried out for 1 hour to obtain a hydrotalcite precursor solution; the precursor solution is transferred to a reaction kettle, hydrothermal treatment is carried out at 120°C for 24 hours to obtain a hydrotalcite filler; after washing the hydrotalcite filler, drying is carried out at 80°C for 12h, and grinding treatment is carried out to obtain a hydrotalcite powder with a particle size of 50-100nm;

[0067] S2: Iron nitrate is mixed with the hydrotalcite powder obtained in step S1, wherein the molar ratio of iron nitrate to aluminum nitrate in step S1 is 1:2, deionized water is added, a sodium hydroxide solution is added to adjust the pH value of the solution to 9, and stirring is carried out for 1 hour to obtain a composite precursor solution; the composite precursor solution is transferred to a reaction kettle, hydrothermal treatment is carried out at 120°C for 24 hours to obtain a composite filler;

[0068] S3: After washing the composite filler, drying is carried out at 80°C for 12h, and grinding treatment is carried out to obtain a composite filler powder with a particle size of 50-100nm;

[0069] S4: The composite filler powder and the PET master batch are mixed according to a mass ratio of 1:49, a film is prepared by melt mixing and spinning, and is dried at 80°C for 2 hours to prepare the sunscreen polyester; wherein the process parameters of melt mixing and spinning are as follows: the spinning temperature is set to 245 o C, the screw rotation speed is set to 10 r / min, and the winding speed of the drum is 600 m / min.

[0070] Comparative Example 4

[0071] The difference between the present comparative example and Example 1 is that the mass ratio of the filler powder to the PET master batch in step S3 is 1:40.

[0072] The performance of the polyester prepared in the above examples and comparative examples is tested, and the testing method is as follows:

[0073] 1. Anti-ultraviolet property: The UPF of the polyester is tested by a UV-visible spectrometer;

[0074] 2. The UV resistance durability: after 50 times of washing, the UPF of the polyester is tested by the UV-visible spectrometer;

[0075] 3. The tear test is carried out according to the test method of GB / T3917, and the test condition of tongue-shaped tearing is selected for the related test.

[0076] The test results are shown in Table 1:

[0077] Table 1

[0078]

[0079] From the data in the above table, it can be seen that the polyester prepared in each embodiment of the present application has excellent UV resistance, and the UV resistance durability is good; at the same time, the sunscreen polyester still has excellent mechanical properties.

[0080] Comparative Example 1 is a blank comparative example, and no sunscreen filler is added, and the UV resistance is poor.

[0081] Comparative Example 2 uses hydrotalcite as a sunscreen filler, and although the UV resistance is improved compared with Comparative Example 1, it is lower than Example 1, and the UV resistance durability is also lower than Example 1.

[0082] Comparative Example 3 is different from Example 1 in that hydrotalcite is first prepared using aluminum nitrate and magnesium nitrate as raw materials, and then the prepared hydrotalcite powder is subjected to hydrothermal treatment with iron nitrate, and the UV resistance of the prepared polyester is obviously decreased.

[0083] Comparative Example 4 increases the addition amount of sunscreen filler compared with Example 1, although the UV resistance is improved, but the mechanical properties are obviously decreased.

[0084] Based on the above ideal embodiments according to the present application, through the above description, relevant personnel can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the contents of the specification, and the technical scope must be determined according to the scope of the claims.

Claims

1. A method for preparing sun-protective polyester, characterized in that... It includes the following steps: S1: Ferric nitrate, aluminum nitrate, and magnesium nitrate were mixed in a molar ratio of 1:2:6, added to deionized water, and the pH of the solution was adjusted to 9 with alkali solution. The mixture was stirred for 1 hour to obtain an iron-containing hydrotalcite precursor solution. The precursor solution was transferred to a reaction vessel and subjected to hydrothermal treatment at 120°C for 24 hours to allow iron atoms to be embedded in the hydrotalcite interlayer in the form of single atoms, thus obtaining an iron single-atom / hydrotalcite sunscreen filler. S2: Grind the iron single-atom / hydrotalcite sunscreen filler to obtain filler powder; S3: Mix the filler powder with PET masterbatch, melt it, and then spin it through the solution to prepare sunscreen polyester.

2. The method for preparing sun-protective polyester as described in claim 1, characterized in that... The particle size of the filler powder in step S2 is 50-100 nm.

3. The method for preparing sun-protective polyester as described in claim 1 or 2, characterized in that... In step S3, the mass ratio of the filler powder to the PET masterbatch is 1:(30-50).

4. A sun-protective polyester, characterized in that... It is prepared by the method for preparing sunscreen polyester as described in any one of claims 1-3.

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