A preparation method of rare earth modified flame retardant material and its application in fabric flame retardancy

Abstract

The present invention provides a method for preparing a rare earth modified flame retardant material and its application in flame retardant fabrics. The method combines hexachlorocyclotriphosphazene with p-hydroxybenzoic acid to form a phenoxy group, and then reacts with a rare earth chloride to obtain a rare earth modified flame retardant material. The method has a simple preparation process, does not require high temperature and high pressure reaction, does not generate pollution, and is easy to scale up production. The present invention also provides a method for preparing flame retardant fibers using the rare earth modified flame retardant material CSHB-X. The rare earth modified flame retardant material has good flame retardant properties on fiber-forming fabrics and can effectively reduce the afterburning time of fiber-forming fabrics.

Description

Technical Field

[0001] The invention belongs to the field of flame-retardant coated textile fabrics, and in particular relates to a preparation method of a rare earth modified flame-retardant material and application thereof in flame-retardant fabrics. Background Art

[0002] The key to manufacturing flame-retardant textiles lies in flame retardants and flame retardant technology. Common flame retardants can be classified into halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, metal hydroxides, etc. according to the flame retardant elements. However, the harmful substances produced by some flame retardants during use can be enriched in organisms and the environment, causing serious impacts on the human body and the natural environment. With the increasing awareness of environmental protection, safety and health, researchers have begun to focus on the research, development and application of environmentally friendly flame retardants. Summary of the invention

[0003] In view of this, the present invention aims to overcome the defects in the prior art and provides a method for preparing a rare earth modified flame retardant material.

[0004] The present invention also aims to provide a method for preparing a flame retardant fiber containing a rare earth modified flame retardant material.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A rare earth modified flame retardant material CSHB-X, the molecular formula of the flame retardant material CSHB-X is , the raw materials in the flame retardant material CSHB-X contain rare earth chloride.

[0007] Furthermore, the raw materials of the flame retardant material CSHB-X include hydroxybenzoic acid, hexachlorocyclotriphosphazene, and rare earth chloride, and the molar ratio thereof is 6:1:6.

[0008] Furthermore, the preparation method of the flame retardant material CSHB-X is:

[0009] (1) Dissolve potassium carbonate and p-hydroxybenzoic acid in tetrahydrofuran and heat in an inert atmosphere;

[0010] (2) slowly dripping hexachlorocyclotriphosphazene into the solution of step (1) to continue the reaction;

[0011] (3) the product obtained in step (2) is vacuum dried, then dissolved in dichloromethane, washed with deionized water, and dried to obtain CSHB;

[0012] (4) Add deionized water to the dried CSHB, heat it, and stir it thoroughly to dissolve it;

[0013] (5) Add rare earth chloride to deionized water and completely dissolve it under stirring;

[0014] (6) Slowly drop the mixed solution of step (5) into the solution of step (4), maintaining the temperature at about 90°C. After the reaction is complete, filter and wash with deionized water and dry to obtain CSHB-X.

[0015] Furthermore, the rare earth chloride in step (5) is any one or more of lanthanum chloride and cerium chloride.

[0016] The rare earth modified flame retardant material CSHB-X is used in flame retardant polyester, polyamide, polylactic acid and other fiber-forming polymers.

[0017] A method for preparing a flame retardant fiber containing the rare earth modified flame retardant material CSHB-X comprises the following steps:

[0018] (A) Rare earth modified flame retardant material CSHB-X and deionized water (2-4):1 were added into a planetary ball mill and ball milled for 3-6 hours.

[0019] (B) After the ball milling, 2-15 wt% of a dispersant is added to the slurry and then the slurry is sand milled in a sand mill for 24 hours to obtain a rare earth modified flame retardant slurry.

[0020] (C) 30-60 parts by weight of rare earth modified flame retardant slurry and 50-80 parts by weight of high molecular polymer are hot mixed, granulated and spun to prepare flame retardant fiber.

[0021] Furthermore, the high molecular polymer in step (C) is any one of PET, PBT, PA6, and PA66.

[0022] Furthermore, the dispersant in step (B) is any one of BYK2013, KH560, and polyethylene glycol.

[0023] The flame retardant fiber preparation method is used in the preparation of clothing products, home textile products, and industrial textiles.

[0024] The rare earth modified flame retardant material CSHB-X provided by the present invention is a phosphine-nitrogen flame retardant, does not contain halogen and antimony substances, is non-toxic and harmless, has good stability, has a simple preparation process, does not require high temperature and high pressure reaction, does not generate pollution, and is easy to scale up production.

[0025] When the fabric containing the rare earth modified flame retardant material CSHB-X burns, it will decompose to produce phosphoric acid, ammonia, etc. These gases will take away a lot of heat, thereby reducing the combustion temperature and achieving a flame retardant effect. These decomposition products can also dilute the oxygen in the air, release non-combustible gases such as nitrogen and carbon dioxide, further reduce the degree of combustion, and play a role in suppressing flames. In addition, it can also prevent oxygen from contacting carbon.

[0026] The flame retardant material provided by the present invention introduces rare earth ions, improves the thermal stability and water resistance of hypophosphite, and at the same time, the organic hypophosphite has a good synergistic effect with solid acid, melamine salt, etc. The rare earth material used in the present invention has a rich energy level structure, the rare earth elements and the phosphine nitrogen compound have a catalytic carbonization effect, the rare earth ions can effectively improve the strength of the carbon layer formed by combustion through ionic crosslinking, and the carbon layer and the inorganic components generated by the degradation of phenoxy cyclotriphosphazene form an organic-inorganic physical barrier layer together, inhibiting the oxygen and energy transmission in the combustion area, thereby effectively improving the flame retardant performance of the fabric.

[0027] The rare earth material used in the present invention has good flame retardant properties on the fiber-forming fabric, and can effectively reduce the afterburning time of the fiber-forming fabric, and the smoldering time is 0s. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0029] Figure 1 This is the Fourier infrared spectrum of the rare earth modified flame retardant material CSHB-X;

[0030] Figure 2 This is the SEM image of the rare earth modified flame retardant material CSHB-X. DETAILED DESCRIPTION

[0031] The following specific descriptions are exemplary and are intended to provide further explanation of the present invention. It should be understood by those skilled in the art that the details and forms of the technical solution of the present invention may be modified or replaced without departing from the spirit and scope of the present invention, but these modifications and replacements fall within the protection scope of the present invention.

[0032] Unless otherwise specified, the test methods used in the following experimental examples are conventional methods.

[0033] Example 1

[0034] Weigh p-hydroxybenzoic acid: hexachlorocyclotriphosphazene: rare earth chloride in a molar ratio of 6:1:6. Dissolve 11.38 g of potassium carbonate and 6.54 g of p-hydroxybenzoic acid in 120 ml of THF. 2 heated to 70°C under atmosphere; 2.49 g of hexachlorocyclotriphosphazene P 3 N 3 Cl 6Slowly drip into the solution and continue the reaction for a certain period of time; vacuum dry the product to remove the solvent, dissolve the obtained solid in dichloromethane, wash the organic phase with deionized water, and then dry to obtain CSHB; add 1 mol of CSHB to 100 ml of deionized water, heat, and stir thoroughly to dissolve; add 6 mol of rare earth chloride (any one of lanthanum chloride and cerium chloride) to 100 ml of deionized water and completely dissolve it under stirring; then slowly drip it into the CSHB solution, keep the temperature at about 90°C, and after the reaction is complete, filter, wash and dry with deionized water to obtain the rare earth modified flame retardant material CSHB-X. Infrared detection of CSHB-X shows that (see Figure 1 ), multiple infrared peaks indicate the successful synthesis of CSHB-X, 1597.14 cm -1 、1501.45 cm -1 and 1421.63 cm -1 Characteristic peak of C6H4; 830.72 cm -1 Indicates the presence of para-substituted benzene; 1008.19 cm -1 and 963.40 cm -1 For POC key; 1159.26 cm -1 and 1270.80 cm -1 P=N bond; 892.15 cm -1 PN key; 1674.92 cm -1 Indicates the presence of formic acid groups; 1509.43 cm -1 、1594.25 cm -1 、1607.9 cm -1 2 are characteristic peaks of benzene ring. The microscopic appearance of CSHB-X is as follows Figure 2 shown.

[0035] The rare earth modified flame retardant material CSHB-X and deionized water (2-4) are added to a planetary ball mill for 3-6 hours. After adding 2-15wt% of dispersant (any one of BYK2013, KH560, polyethylene glycol) to the milled slurry, it is sand-milled in a sand mill for 24 hours to obtain a rare earth modified flame retardant slurry. 30-60 parts by weight of rare earth modified flame retardant slurry and 50-80 parts by weight of high molecular polymer (any one of PET, PBT, PA6, PA66) are prepared by hot mixing, granulation, and spinning to obtain flame retardant functional fiber fabric A.

[0036] Comparative Example 1

[0037] The preparation method of the fabric in this embodiment is the same as that in Embodiment 1, except that p-hydroxybenzoic acid, hexachlorotriphosphazene and rare earth chloride are added in a molar ratio of 6:1:3 when preparing the rare earth flame retardant material, and flame retardant functional fiber-forming fabric B is obtained.

[0038] Comparative Example 2

[0039] The preparation method of the fabric in this embodiment is the same as that in Embodiment 1, except that p-hydroxybenzoic acid, hexachlorotriphosphazene and rare earth chloride are added in a molar ratio of 3:1:3 when preparing the rare earth flame retardant material, and flame retardant functional fiber-forming fabric C is obtained.

[0040] Comparative Example 3

[0041] The preparation method of the fabric in this embodiment is the same as that in embodiment 1, except that the flame retardant powder is replaced with decabromodiphenyl ether when preparing the fiber-forming fabric, and a flame retardant functional fiber-forming fabric D is obtained.

[0042] The LOI index of the fabrics obtained in Example 1 and Comparative Examples 1-3 was tested, and the flame retardant properties were tested on a vertical combustion instrument. The results are shown in the following table:

[0043]

[0044] From the comparison results of Example 1 and Comparative Examples 1-3, it can be seen that the introduction of rare earth elements effectively increases the LOI oxygen index value and significantly improves the flame retardant effect.

[0045] From the comparison results of Example 1 and Comparative Examples 1-3, it can be seen that the increase of rare earth elements can improve the flame retardant effect of the fabric, and the best effect is achieved when the molar ratio of p-hydroxybenzoic acid to rare earth chloride is 1:1.

[0046] The flame retardant functional fiber fabric prepared in Example 1 has the best flame retardant performance, and the UL94 combustion grade reaches V-0. The after-flaming time of the fabric prepared in the present invention in the vertical combustion test is less than 25s.

[0047] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A rare earth modified flame retardant material CSHB-X, characterized in that: The molecular formula of the flame retardant material CSHB-X is The raw material of the flame retardant material CSHB-X contains rare earth chloride, and the rare earth chloride is any one or more of lanthanum chloride and cerium chloride.

2. The rare earth modified flame retardant material CSHB-X according to claim 1, characterized in that the preparation method of the flame retardant material CSHB-X is: (1) Dissolve potassium carbonate and p-hydroxybenzoic acid in tetrahydrofuran and heat in an inert atmosphere; (2) slowly dripping hexachlorocyclotriphosphazene into the solution of step (1) to continue the reaction; (3) the product obtained in step (2) is vacuum dried, then dissolved in dichloromethane, washed with deionized water, and dried to obtain CSHB; (4) Add deionized water to the dried CSHB, heat it, and stir it thoroughly to dissolve it; (5) Add rare earth chloride to deionized water and completely dissolve it under stirring; (6) Slowly drop the mixed solution of step (5) into the solution of step (4), maintaining the temperature at 90°C. After the reaction is complete, filter and wash with deionized water and dry to obtain CSHB-X.

3. The rare earth modified flame retardant material CSHB-X according to claim 2, characterized in that: In the preparation method of the flame retardant material CSHB-X, the molar ratio of hydroxybenzoic acid, hexachlorocyclotriphosphazene and rare earth chloride is 6:1:

6.

4. Use of the rare earth modified flame retardant material CSHB-X as described in any one of claims 1 to 3 in flame retardant polyester, polyamide and polylactic acid.

5. A method for preparing a flame retardant fiber containing the rare earth modified flame retardant material CSHB-X described in any one of claims 1 to 3, characterized in that: The following steps are involved: (A) Add the rare earth modified flame retardant material CSHB-X and deionized water in a ratio of 2-4:1 and add them into a planetary ball mill for 3-6 hours; (B) adding 2-15 wt% of a dispersant to the ball-milled slurry and then sand-milling the slurry in a sand mill for 24 hours to obtain a rare earth modified flame retardant slurry; (C) 30-60 parts by weight of rare earth modified flame retardant slurry and 50-80 parts by weight of high molecular polymer are taken, and flame retardant fibers are prepared by hot mixing, granulation and spinning.

6. The method for preparing the flame-retardant fiber according to claim 5, characterized in that: The high molecular polymer in step (C) is any one of PET, PBT, PA6 and PA66.

7. The method for preparing the flame-retardant fiber according to claim 5, characterized in that: The dispersant in step (B) is any one of BYK2013, KH560 and polyethylene glycol.

8. Use of the flame-retardant fiber according to claim 5 in the preparation of clothing, home textile products, and industrial textiles.

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