Phosphorus-nitrogen rare earth compound and rare earth flame-retardant fabric

Abstract

The invention provides a phosphorus-nitrogen rare earth compound and a rare earth flame-retardant fabric, the fabric comprises a flame-retardant coating primer and a flame-retardant coating surface adhesive, the flame-retardant coating primer is prepared from the following raw materials in parts by weight: 30-35 parts of polyurethane emulsion, 15-50 parts of the phosphorus-nitrogen rare earth compound according to claim 1, 5-25 parts of decabromodiphenyl ethane, 5-25 parts of N, N-dimethylformamide, 5-25 parts of N, N-dimethylformamide, 5-25 parts of N, N-dimethylformamide, 5-25 parts of N, N-dimethylformamide, 5-25 parts of N, N-dimethylformamide, 5-25 parts of N, N The adhesive comprises the following components in parts by weight: 20-30 parts of N, N-dimethylformamide, 1-3 parts of a bridging agent, 1-1.5 parts of a cross-linking agent and 0.2-1.5 parts of an accelerant. The phosphorus-nitrogen rare earth compound disclosed by the invention has excellent synergistic flame-retardant property, can replace halogen and antimony-containing compounds in a flame-retardant system, and reduces the smoke amount and the generation of harmful gases; under specific reaction conditions, amino groups and carboxyl groups of reactants are combined in an ionic state form, a para-position structure of p-hydroxyphenylphosphoric acid has relatively high structural stability, and a specific triazine ring structure of melamine can effectively improve the thermal stability of the fabric.

Description

Technical Field

[0001] The invention belongs to the field of textiles, and in particular relates to a phosphorus-nitrogen rare earth compound and a rare earth flame-retardant fabric. Background Art

[0002] Halogen flame retardants have many advantages such as excellent comprehensive performance and high cost performance. They are widely used in flame retardant materials in industries such as construction, transportation, electronic appliances and textiles. They are one of the most widely used organic flame retardants in the world. Due to the chemical properties of the halogen element itself, halogen flame retardants also expose many shortcomings during use. Halogen flame retardants have poor thermal stability and will decompose under high temperature and open flame conditions to produce hydrogen halide gas and thick smoke. In a fire, smoke is the most direct factor leading to human suffocation and casualties.

[0003] Phosphorus-nitrogen intumescent flame retardant is a flame retardant with phosphorus and nitrogen as the main components. Compared with common halogen flame retardants and antimony-containing flame retardants, it has the advantages of less smoke, less toxic gas generation, anti-melting droplets, and shows good flame retardant properties. Intumescent flame retardant is usually composed of three sources: acid source, carbon source and gas source. When the material burns, the acid source and carbon source quickly undergo esterification and cross-linking reactions to form a molten carbon layer; the gas source releases inert non-combustible gases such as nitrogen and water vapor to make the molten carbon foam and expand, while diluting the oxygen concentration around the burning object; the synergistic effect of the three sources forms a dense and porous intumescent carbon layer on the surface of the material, blocking heat and oxygen, thereby achieving a flame retardant effect.

[0004] Rare earth is a general term for 17 chemical elements in group IIIB of the periodic table of chemical elements. 0－14 5d 1 －10 6s 2 The electronic layer structure makes it non-toxic, environmentally friendly, heat-resistant, and catalytic esterification and dehydrogenation reactions, and it is widely used in the chemical industry. Since the carbonization process of polymer combustion is itself an esterification and dehydrogenation process, the dense carbon layer can effectively prevent the spread of flames. Summary of the invention

[0005] In view of this, the present invention aims to overcome the defects in the prior art and proposes a phosphorus-nitrogen rare earth compound and a rare earth flame retardant fabric.

[0006] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0007] A phosphorus-nitrogen rare earth compound, the structural formula of the compound is shown in formula (I):

[0008]

[0009] Among them, Re is a rare earth ion.

[0010] Furthermore, the rare earth ion is at least one of lanthanum ion, cerium ion or yttrium ion.

[0011] The method for preparing the phosphorus-nitrogen rare earth compound comprises the following steps:

[0012] (1) adding p-carboxyphenylphosphonic acid to deionized water, stirring and dispersing the water under heating until the solution is clear and colorless, thereby obtaining a p-carboxyphenylphosphonic acid solution;

[0013] (2) adding rare earth nitrate into deionized water and stirring to disperse the mixture to obtain a rare earth nitrate solution;

[0014] (3) adding the rare earth nitrate solution dropwise to the p-carboxyphenylphosphonic acid solution, reacting under heating conditions to obtain a reaction solution;

[0015] (4) adding melamine to the reaction solution and reacting under heating conditions; after the reaction is completed, washing, filtering, drying and crushing the reaction product to obtain the phosphorus-nitrogen rare earth compound.

[0016] Furthermore, the molar ratio of the carboxyphenylphosphonic acid, the rare earth nitrate and the melamine is 3:1:3; and the rare earth nitrate is at least one of lanthanum nitrate, cerium nitrate or yttrium nitrate.

[0017] Furthermore, the temperature of the heating step in step (1) is 85-95°C; the temperature of the heating step in step (3) is 90-95°C, and the reaction time is 3-6 hours; the temperature of the heating step in step (4) is 95-100°C, and the reaction time is 5-8 hours.

[0018] A rare earth flame retardant fabric comprises a flame retardant coating primer and a flame retardant coating top glue, wherein the flame retardant coating primer is made of the following raw materials in parts by weight: 30-35 parts of polyurethane emulsion, 15-50 parts of phosphorus nitrogen rare earth compound, 5-25 parts of decabromodiphenylethane, 20-30 parts of N,N-dimethylformamide, 1-3 parts of bridging agent, 1-1.5 parts of crosslinking agent and 0.2-1.5 parts of accelerator.

[0019] Furthermore, the flame retardant coating surface adhesive is made of the following raw materials in parts by weight: 1-3 parts of matting powder, 60-64 parts of polyurethane emulsion, and 30-38 parts of N,N-dimethylformamide.

[0020] The method for preparing the rare earth flame retardant fabric comprises the following steps:

[0021] Step 1 is to fully mix the phosphorus nitrogen rare earth compound, N,N-dimethylformamide, polyurethane emulsion, decabromodiphenylethane, a bridging agent, a crosslinking agent and an accelerator to obtain a flame retardant coating primer, apply the flame retardant coating primer on a sample cloth, and then dry and cure it to obtain a flame retardant coating primer coating;

[0022] Step 2 is to mix the matting powder, polyurethane emulsion and N,N-dimethylformamide to obtain a flame retardant coating surface adhesive, apply the flame retardant coating surface adhesive on the flame retardant coating base adhesive coating, and then dry and solidify to form a flame retardant coating surface adhesive coating to obtain the rare earth flame retardant fabric.

[0023] Furthermore, the viscosity of the flame retardant coating primer in step 1 is 18000-20000cps; the viscosity of the flame retardant coating topcoat in step 2 is 18000-20000cps.

[0024] Furthermore, the sum of the thickness of the flame retardant coating primer coating and the flame retardant coating top coating is 0.1-0.2 mm.

[0025] Furthermore, the bridging agent in step 1 is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or dicyclohexylmethane diisocyanate; and the accelerator in step 1 is at least one of triethylenediamine, A-1 or A-33.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] The phosphorus-nitrogen rare earth compound of the present invention has excellent synergistic flame retardant performance, can replace halogen and antimony-containing compounds in the flame retardant system, and reduce the amount of smoke and the generation of harmful gases; under specific reaction conditions, the amino group and carboxyl group of the reactant are combined in an ionic form, the para-structure of hydroxyphenyl phosphate has a strong structural stability, and the unique triazine ring structure of melamine can effectively improve the thermal stability of the fabric. At the same time, it has a high nitrogen content, low toxicity, and is non-flammable. When heated, it generates non-flammable gases such as nitrogen and water vapor, which can provide a gas phase flame retardant mechanism, and can synergize with an acid source and a carbon source to form an expanded carbon layer, thereby achieving the flame retardant effects of heat insulation, oxygen isolation, smoke suppression, and anti-melting droplet.

[0028] The unique 4f of rare earth elements 0－14 5d 1－10 6s 2 The electronic layer structure makes it non-toxic, environmentally friendly, heat-resistant, and catalytic esterification and dehydrogenation reactions. The polymer combustion process is an esterification and dehydrogenation reaction. It provides a catalytic carbonization effect during the polymer combustion process, accelerates the formation of the expanded carbon layer, and can effectively reduce the fabric afterburning time, reduce the flame spread speed and diffusion range.

[0029] The phosphorus-nitrogen rare earth compound of the present invention improves the thermal stability of the phosphorus-nitrogen flame retardant, reduces the spread of flames, reduces molten droplets, and simultaneously reduces the amount of halogen and antimony-containing compounds added to the flame retardant, and reduces the amount of harmful gases released during combustion.

[0030] The preparation method of the present invention does not require high temperature and high pressure reaction, has a high reactant yield, does not use organic solvents during the reaction, and meets the requirements of green environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a SEM image of the phosphorus-nitrogen rare earth compound described in Example 1 of the present invention;

[0032] Figure 2 Thermogravimetric curve (30-800° C.) of the phosphorus-nitrogen rare earth compound described in Example 1 of the present invention;

[0033] Figure 3 This is a Fourier transform infrared spectrum of the phosphorus-nitrogen rare earth compound described in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0035] The present invention will be described in detail below with reference to the embodiments.

[0036] Example 1

[0037] A method for preparing a phosphorus-nitrogen rare earth compound comprises the following steps:

[0038] (1) adding 1.5 mol of p-carboxyphenylphosphonic acid to 350 ml of deionized water, stirring and dispersing the mixture under heating until the solution is clear and colorless, thereby obtaining a p-carboxyphenylphosphonic acid solution;

[0039] (2) adding 0.5 mol of cerium nitrate into 120 ml of deionized water and stirring to disperse the mixture to obtain a cerium nitrate solution;

[0040] (3) adding the cerium nitrate solution dropwise to the p-carboxyphenylphosphonic acid solution, reacting at 90° C. for 4 hours to obtain a reaction solution;

[0041] (4) adding melamine to the reaction solution and reacting at 95° C. for 6 hours. After the reaction is completed, washing, filtering, drying and crushing the reaction product to obtain the phosphorus-nitrogen rare earth compound.

[0042] A method for preparing a rare earth flame retardant fabric comprises the following steps:

[0043] Step 1 is to fully mix 30 parts of phosphorus nitrogen rare earth compound, 10 parts of decabromodiphenylethane, 25 parts of N,N-dimethylformamide, 30 parts of polyurethane emulsion, 2 parts of toluene diisocyanate and 0.8 parts of A-33 to obtain a flame retardant coating primer, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating primer on the sample cloth, and then dry and cure it to obtain a flame retardant coating primer coating;

[0044] Step 2 is to mix 2.4 parts of matting powder, 62 parts of polyurethane emulsion and 36 parts of N,N-dimethylformamide to obtain a flame retardant coating top coat, use a coating rod with a diameter of 0.5 cm to coat the flame retardant coating top coat on the flame retardant coating base coat, and then dry and cure to form a flame retardant coating top coat to obtain the rare earth flame retardant fabric.

[0045] Comparative Example 1

[0046] A method for preparing a phosphorus-nitrogen compound comprises the following steps:

[0047] (1) adding 1.5 mol of p-carboxyphenylphosphonic acid to 350 ml of deionized water, stirring and dispersing the mixture under heating until the solution is clear and colorless, thereby obtaining a p-carboxyphenylphosphonic acid solution;

[0048] (2) adding 1.5 mol of melamine to the carboxyphenylphosphonic acid solution, reacting at 95° C. for 6 hours, and after the reaction is completed, washing, filtering, drying, and crushing the reaction product to obtain the phosphorus nitrogen compound.

[0049] A method for preparing a flame retardant fabric comprises the following steps:

[0050] Step 1 is to fully mix 30 parts of phosphorus nitrogen rare earth compound, 10 parts of decabromodiphenylethane, 25 parts of N,N-dimethylformamide, 30 parts of polyurethane emulsion, 2 parts of toluene diisocyanate and 0.8 parts of A-33 to obtain a flame retardant coating primer, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating primer on the sample cloth, and then dry and cure it to obtain a flame retardant coating primer coating;

[0051] Step 2 is to mix 2.4 parts of matting powder, 62 parts of polyurethane emulsion and 36 parts of N,N-dimethylformamide to obtain a flame retardant coating top glue, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating top glue on the flame retardant coating base glue coating, and then dry and cure it to form a flame retardant coating top glue coating to obtain the flame retardant fabric.

[0052] Comparative Example 2

[0053] A method for preparing a phosphorus-nitrogen rare earth compound comprises the following steps:

[0054] (1) adding 1.5 mol of p-carboxyphenylphosphonic acid to 350 ml of deionized water, stirring and dispersing the mixture under heating until the solution is clear and colorless, thereby obtaining a p-carboxyphenylphosphonic acid solution;

[0055] (2) adding 0.5 mol of cerium nitrate into 120 ml of deionized water and stirring to disperse the mixture to obtain a cerium nitrate solution;

[0056] (3) adding the cerium nitrate solution dropwise to the p-carboxyphenylphosphonic acid solution, reacting at 90° C. for 4 hours, and after the reaction is completed, washing, filtering, drying, and crushing the reaction product to obtain the phosphorus-nitrogen rare earth compound.

[0057] A method for preparing a rare earth flame retardant fabric comprises the following steps:

[0058] Step 1 is to fully mix 30 parts of phosphorus nitrogen rare earth compound, 10 parts of decabromodiphenylethane, 25 parts of N,N-dimethylformamide, 30 parts of polyurethane emulsion, 2 parts of toluene diisocyanate and 0.8 parts of A-33 to obtain a flame retardant coating primer, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating primer on the sample cloth, and then dry and cure it to obtain a flame retardant coating primer coating;

[0059] Step 2 is to mix 2.4 parts of matting powder, 62 parts of polyurethane emulsion and 36 parts of N,N-dimethylformamide to obtain a flame retardant coating top coat, use a coating rod with a diameter of 0.5 cm to coat the flame retardant coating top coat on the flame retardant coating base coat, and then dry and cure to form a flame retardant coating top coat to obtain the rare earth flame retardant fabric.

[0060] Comparative Example 3

[0061] A method for preparing a flame retardant fabric comprises the following steps:

[0062] Step 1 is to fully mix 30 parts of ammonium polyphosphate, 10 parts of decabromodiphenylethane, 25 parts of N,N-dimethylformamide, 30 parts of polyurethane emulsion, 2 parts of toluene diisocyanate, 1.2 parts of A-33 and 0.8 parts of accelerator to obtain a flame retardant coating primer, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating primer on the sample cloth, and then dry and cure it to obtain a flame retardant coating primer coating;

[0063] Step 2 is to mix 2.4 parts of matting powder, 62 parts of polyurethane emulsion and 36 parts of N,N-dimethylformamide to obtain a flame retardant coating top glue, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating top glue on the flame retardant coating base glue coating, and then dry and cure it to form a flame retardant coating top glue coating to obtain the flame retardant fabric.

[0064] Comparative Example 4

[0065] A method for preparing a flame retardant fabric comprises the following steps:

[0066] Step 1 is to fully mix 10 parts of decabromodiphenylethane, 25 parts of N,N-dimethylformamide, 30 parts of polyurethane emulsion, 2 parts of toluene diisocyanate and 0.8 parts of A-33 to obtain a flame retardant coating primer, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating primer on the sample cloth, and then dry and cure it to obtain a flame retardant coating primer coating;

[0067] Step 2 is to mix 2.4 parts of matting powder, 62 parts of polyurethane emulsion and 36 parts of N,N-dimethylformamide to obtain a flame retardant coating top glue, use a coating rod with a diameter of 0.5 cm to apply the flame retardant coating top glue on the flame retardant coating base glue coating, and then dry and cure it to form a flame retardant coating top glue coating to obtain the flame retardant fabric.

[0068] The flame retardant coated fabrics prepared in Example 1 and Comparative Examples 1-5 were subjected to performance tests: the flame retardant properties of the flame retardant coated fabrics obtained above were tested by a limiting oxygen index instrument and a vertical combustion tester, as shown in Table 1.

[0069] Table 1 Performance results

[0070]

[0071] As shown in Table 1, it can be seen from the results of Example 1 and the comparative examples that the introduction of rare earth phosphorus nitrogen compounds effectively increases the limiting oxygen index of the material, and the flame retardant effect is significantly improved.

[0072] In comparative example 1, there is no coordinated rare earth ion, and the catalytic carbonization effect is lacking, so the afterburning time is increased, the longitudinal and lateral damage lengths are increased, and the flame diffusion is more obvious.

[0073] In Comparative Example 2, melamine was not introduced, the limiting oxygen index dropped significantly, the afterflaming time increased significantly, the damage was more obvious, and the thermal stability of the material was poor.

[0074] Comparative Example 3 uses common phosphorus-nitrogen compounds, but the carbonization effect is poor and the molten droplets will ignite the cotton pad.

[0075] In comparative example 4, the limiting oxygen index was the lowest without adding rare earth phosphorus-nitrogen compounds, and the UL94 combustion level was reduced to V-2, with obvious damage.

[0076] 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 principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A phosphorus-nitrogen rare earth compound, characterized in that: The structural formula of the compound is shown in formula (I): Among them, Re is a rare earth ion.

2. The method for preparing the phosphorus-nitrogen rare earth compound according to claim 1, characterized in that: The steps include: (1) adding p-carboxyphenylphosphonic acid to deionized water, stirring and dispersing the water under heating until the solution is clear and colorless, thereby obtaining a p-carboxyphenylphosphonic acid solution; (2) adding rare earth nitrate into deionized water and stirring to disperse the mixture to obtain a rare earth nitrate solution; (3) adding the rare earth nitrate solution dropwise to the p-carboxyphenylphosphonic acid solution, reacting under heating conditions to obtain a reaction solution; (4) adding melamine to the reaction solution and reacting under heating conditions; after the reaction is completed, washing, filtering, drying and crushing the reaction product to obtain the phosphorus-nitrogen rare earth compound.

3. The method for preparing a phosphorus-nitrogen rare earth compound according to claim 2, characterized in that: The molar ratio of the carboxyphenylphosphonic acid, the rare earth nitrate and the melamine is 3:1:3; the rare earth nitrate is at least one of lanthanum nitrate, cerium nitrate or yttrium nitrate.

4. The method for preparing a phosphorus-nitrogen rare earth compound according to claim 2, characterized in that: The temperature of the heating step in step (1) is 85-95°C; the temperature of the heating step in step (3) is 90-95°C, and the reaction time is 3-6 hours; the temperature of the heating step in step (4) is 95-100°C, and the reaction time is 5-8 hours.

5. A rare earth flame retardant fabric, characterized in that: The fabric comprises a flame retardant coating primer and a flame retardant coating top glue, wherein the flame retardant coating primer is made of the following raw materials in parts by weight: 30-35 parts of polyurethane emulsion, 15-50 parts of the phosphorus nitrogen rare earth compound according to claim 1, 5-25 parts of decabromodiphenylethane, 20-30 parts of N,N-dimethylformamide, 1-3 parts of a bridging agent, 1-1.5 parts of a crosslinking agent, and 0.2-1.5 parts of an accelerator.

6. The rare earth flame retardant fabric according to claim 5, characterized in that: The flame retardant coating surface adhesive is made of the following raw materials in parts by weight: 1-3 parts of matting powder, 60-64 parts of polyurethane emulsion, and 30-38 parts of N,N-dimethylformamide.

7. The method for preparing the rare earth flame retardant fabric according to claim 5 or 6, characterized in that: The steps include: Step 1 is to fully mix the phosphorus-nitrogen rare earth compound, N,N-dimethylformamide, polyurethane emulsion, decabromodiphenylethane, a bridging agent and an accelerator to obtain a flame retardant coating primer, apply the flame retardant coating primer on a sample cloth, and then dry and cure to obtain a flame retardant coating primer coating; Step 2 is to mix the matting powder, polyurethane emulsion and N,N-dimethylformamide to obtain a flame retardant coating surface adhesive, apply the flame retardant coating surface adhesive on the flame retardant coating base adhesive coating, and then dry and solidify to form a flame retardant coating surface adhesive coating to obtain the rare earth flame retardant fabric.

8. The method for preparing the rare earth flame retardant fabric according to claim 7, characterized in that: The viscosity of the flame retardant coating primer in step 1 is 18000-20000cps; the viscosity of the flame retardant coating topcoat in step 2 is 18000-20000cps.

9. The method for preparing the rare earth flame retardant fabric according to claim 7, characterized in that: The sum of the thickness of the flame retardant coating primer coating and the flame retardant coating top coating is 0.1-0.2 mm.

10. The method for preparing rare earth flame retardant fabric according to claim 7, characterized in that: The bridging agent in step 1 is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or dicyclohexylmethane diisocyanate; the accelerator in step 1 is at least one of triethylenediamine, A-1 or A-33.

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