Ethanol-soluble cotton fabric halogen-free flame-retardant spray and preparation method thereof

Abstract

The invention belongs to the technical field of textile material treatment, and relates to an ethanol-soluble cotton fabric halogen-free flame-retardant spray and a preparation method thereof, in particular to a halogen-free flame-retardant spray which can be dissolved by ethanol and the concentration of an ethanol solution can be flexibly adjusted so as to realize different degrees of flame-retardant effects, and a preparation method of the halogen-free flame-retardant spray. The manufacturing cost is low, the production process is simple, the flame-retardant effect is good, and the appearance visual effect of the cotton fabric is not affected after the flame retardant is sprayed. By adjusting the concentration of the ethanol solution, the spraying agent can achieve different degrees of flame retardant effects, and more flexibility is provided for practical application of the spraying agent.

Description

Technical Field

[0001] The present invention belongs to the technical field of textile material processing, and relates to a halogen-free flame retardant spray and a preparation method thereof, and in particular to a halogen-free flame retardant spray that can be dissolved in ethanol and the concentration of the ethanol solution can be flexibly adjusted to achieve different degrees of flame retardant effect, and a preparation method thereof. Background Art

[0002] Cotton fabric, a popular natural fiber material, is widely used in a variety of applications, including clothing and home furnishings, thanks to its excellent breathability and comfort. However, its flammability poses certain safety risks, especially in situations with high fire risk. When exposed to a fire source, cotton fabric burns rapidly, potentially causing and spreading a fire. This, to a certain extent, limits its use in certain areas. With the development of society, the improvement of people's living standards, and the increasing demand for safety, the demand for flame-retardant treatment of cotton fabrics is also increasing.

[0003] There are many traditional flame retardant treatment methods for cotton fabrics, which are often used in daily life, such as dipping and drying, padding and baking, coating, microencapsulation technology, sol-gel technology, and layer-by-layer self-assembly technology.

[0004] However, although these methods can improve the flame retardancy of cotton fabrics to a certain extent, they generally have disadvantages such as low efficiency, high cost, environmental burden, or impact on the original properties of the fabric. For example, although the immersion drying method is simple to operate, the high temperature treatment may damage the texture of the cotton fabric; the padding and baking method is complicated to process, requires a large amount of equipment and space, consumes a lot of water, and requires subsequent treatment such as drying after padding, which increases energy consumption and cost; the coating method has a limited scope of application and is not conducive to large-scale practical application and promotion; and although microcapsule technology and layer-by-layer self-assembly technology provide better durability, their preparation process is complicated. In short, traditional cotton fabric flame retardant methods generally have problems such as inefficient processing, lack of convenience, adverse effects on cotton fabric performance, and high cost. Therefore, the market urgently needs a new flame retardant treatment method for cotton fabrics, which is not only efficient and environmentally friendly, but also more convenient to use. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide an ethanol-soluble halogen-free flame retardant spray for cotton fabrics and a preparation method thereof, so as to solve the technical problems of low efficiency and insufficient convenience in the existing cotton fabric flame retardant technology.

[0006] It should be noted that the present invention aims to provide an ethanol-soluble halogen-free flame retardant spray for cotton fabrics, which significantly improves the flame retardant properties of cotton fabrics through a simple and efficient treatment method, while not affecting the visual appearance of the cotton fabrics after spraying. The present invention can achieve different degrees of flame retardant effects by adjusting the concentration of the ethanol solution, thereby providing more flexibility and selectivity for practical applications. In addition, the use of ethanol solvent not only allows for rapid preparation, but also avoids the use of other toxic solvents.

[0007] The first technical purpose of the present invention is to provide an ethanol-soluble halogen-free flame retardant spray for cotton fabrics, wherein the halogen-free flame retardant spray is prepared by catalytic cross-linking reaction of hydroxyethyl methacrylate, sodium vinyl sulfonate, and 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate in a reaction solvent; wherein the structural formula of the halogen-free flame retardant spray is as follows:

[0008]

[0009] Among them, the values ​​of x, y, and z are determined according to the required performance, and the value range is 0≤x≤1; 0≤y≤1; 0≤z≤1.

[0010] Preferably, the 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate is obtained by reacting hydroxyethyl methacrylate and diphenylphosphinyl chloride; the structural formula of the 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate is as follows:

[0011]

[0012] Preferably, the weight ratio of hydroxyethyl methacrylate, sodium vinyl sulfonate and diphenylphosphinyl chloride is 0-20:0-10:0-30.

[0013] It should be noted that the hydroxyethyl methacrylate, sodium vinyl sulfonate and diphenylphosphinyl chloride can react with each other alone, but the amounts of all components cannot be zero.

[0014] Preferably, the catalyst is 4-(dimethylamino)pyridine; and the weight ratio of the catalyst to hydroxyethyl methacrylate is 1 to 5:100.

[0015] Preferably, the cross-linking agent is azobisisobutyronitrile; and the weight ratio of the cross-linking agent to hydroxyethyl methacrylate is 1 to 5:100.

[0016] Preferably, the reaction solvent is ethanol; the volume ratio of the solvent to the flame retardant is 1 to 100:1.

[0017] The second technical object of the present invention is to provide a method for preparing the ethanol-soluble halogen-free flame retardant spray for cotton fabrics as described above, wherein the method is specifically:

[0018] Hydroxyethyl methacrylate, sodium vinyl sulfonate, 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate and ethanol were added to a reactor, stirred and mixed uniformly under nitrogen protection, and heated to 45° C. to obtain a base material;

[0019] Mix the base material and the cross-linking agent, react at 60-70°C for 14-20 hours under nitrogen protection, and discharge the material after the reaction is completed.

[0020] Furthermore, the preparation operation of the 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate is as follows;

[0021] Diphenylphosphinyl chloride is dissolved in an anhydrous organic solvent such as dichloromethane, ethyl acetate, tetrahydrofuran, etc., and an excess of an acid-binding agent such as triethylamine and pyridine and a catalyst 4-(dimethylamino)pyridine are added. Then, dried hydroxyethyl methacrylate is added dropwise under anaerobic conditions, and the reaction temperature is maintained below 20°. The reaction is continued until the reaction is complete as determined by detection, and the solid by-product produced is removed by filtration. The reaction solvent is removed by low-temperature rotary evaporation to obtain the 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate.

[0022] It can be seen from the above technical solution that, compared with the prior art, the beneficial effects of the present invention are:

[0023] 1) The invention has low production cost and simple production process, and the flame retardant spray is synthesized in one step, has good flame retardant effect, and does not affect the appearance and visual effect of cotton fabric after spraying the flame retardant.

[0024] 2) When using the flame retardant spray of the present invention, it is only necessary to spray the spray evenly on the surface of the cotton fabric and wait for it to dry naturally or after light drying, the cotton fabric can obtain a significant flame retardant effect.

[0025] 3) By adjusting the comonomer ligand and the spray concentration, the spray of the present invention can achieve different degrees of flame retardancy, providing greater flexibility in its practical application. This method is not only simple to operate but also low in cost, making it suitable for large-scale industrial production and household use. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0027] Figure 1The invention provides a flame retardant intermediate 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate with a nuclear magnetic hydrogen spectrum and a nuclear magnetic phosphorus spectrum.

[0028] Figure 2 The flame retardant provided by the present invention has a nuclear magnetic hydrogen spectrum and a nuclear magnetic phosphorus spectrum.

[0029] Figure 3 The infrared spectra of hydroxyethyl methacrylate, diphenylphosphinyl chloride, and 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate provided by the present invention are shown. DETAILED DESCRIPTION

[0030] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0031] The term "embodiment" is used herein specifically to describe any embodiment as "exemplary," and should not be construed as superior or preferable to other embodiments. Performance indicators in the embodiments of this application were tested using conventional testing methods in the art, unless otherwise specified. It should be understood that the terms used in this application are intended solely to describe specific implementations and are not intended to limit the disclosure herein.

[0032] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as commonly understood by ordinary technicians in the technical field to which this application belongs; other experimental methods and technical means not specifically specified in this application refer to experimental methods and technical means commonly used by ordinary technicians in this field.

[0033] In order to better illustrate the content of this application, numerous specific details are provided in the specific examples below. It should be understood by those skilled in the art that this application can be implemented without certain specific details. In the examples, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail in order to highlight the main purpose of this application.

[0034] Under the premise of no conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solutions belong to the contents disclosed in the embodiments of this application.

[0035] The invention discloses an ethanol-soluble halogen-free flame retardant spray for cotton fabrics and a preparation method thereof.

[0036] For a better understanding of the present invention, the present invention is further specifically described below through the following examples, but it should not be understood as limiting the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above invention content are also considered to fall within the scope of protection of the present invention.

[0037] The suppliers of the raw materials of the present invention are:

[0038] Hydroxyethyl methacrylate: Shanghai MacLean Biochemical Technology Co., Ltd. (Shanghai, China);

[0039] Sodium vinyl sulfonate: Beijing Yinuokai Technology Co., Ltd. (Beijing, China);

[0040] Diphenylphosphine chloride: Shanghai Titan Technology Co., Ltd. (Shanghai, China);

[0041] 4-(Dimethylamino)pyridine: Shanghai MacLean Biochemical Technology Co., Ltd. (Shanghai, China);

[0042] Azobisisobutyronitrile: Shanghai MacLean Biochemical Technology Co., Ltd. (Shanghai, China);

[0043] Example

[0044] Hydroxyethyl methacrylate, sodium vinyl sulfonate, 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate and ethanol were added to a reactor, stirred and mixed uniformly under nitrogen protection, and heated to 45° C. to obtain a base material;

[0045] The base material and azobisisobutyronitrile are mixed, reacted at 60-70° C. for 14-20 hours under nitrogen protection, and the material is discharged after the reaction is completed to obtain the ethanol-soluble halogen-free flame retardant spray for cotton fabrics.

[0046] The recipes of the various embodiments are shown in Table 1;

[0047] Table 1 Recipe Unit: g

[0048]

[0049] Comparative Example 1

[0050] The same as Example 1, except that hydroxyethyl methacrylate, diphenylphosphinyl chloride, and 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate were not added.

[0051] Performance Testing

[0052] Vertical burning test:

[0053] The sprays obtained in Examples 1 to 8 and Comparative Example 1 were sprayed on cotton fabric at room temperature. The size of the cotton fabric was 8.9 cm × 30 cm. The cotton fabric was subjected to vertical combustion flame retardancy tests. The flame was ignited for 12 seconds and then the fire source was evacuated. The self-extinguishing time, smoldering time, whether the cotton was ignited, and the combustion level were recorded.

[0054] The test results can be found in Table 2;

[0055] Table 2 Test results

[0056] Implementation / Comparative Example Self-extinguishing time Smoldering Time Whether it ignites Combustion level Example 1 7s 3s no B2 Example 2 18s 0s no B2 Example 3 9s 0s no B2 Example 4 3s 0s no B1 Example 5 1s 0s no B1 Example 6 1s 0s no B1 Example 7 2s 0s no B1 Example 8 1s 0s no B1 Comparative Example 1 7s 26s no B2

[0057] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An ethanol-soluble halogen-free flame retardant spray for cotton fabric, characterized in that: The halogen-free flame retardant spray is prepared by catalytic cross-linking reaction of hydroxyethyl methacrylate, sodium vinyl sulfonate, and 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate in a reaction solvent; wherein the structural formula of the halogen-free flame retardant spray is as follows: Among them, the values ​​of x, y, and z are determined according to the required performance, and the value range is 0≤x≤1; 0≤y≤1; 0≤z≤1.

2. The ethanol-soluble halogen-free flame retardant spray for cotton fabric according to claim 1, characterized in that: The 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate is obtained by reacting hydroxyethyl methacrylate and diphenylphosphinyl chloride; the structural formula of the 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate is as follows:

3. The ethanol-soluble halogen-free flame retardant spray for cotton fabric according to claim 1, characterized in that: The weight ratio of hydroxyethyl methacrylate, sodium vinyl sulfonate and 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate is 0-20:0-10:0-30.

4. The ethanol-soluble halogen-free flame retardant spray for cotton fabric according to claim 1, characterized in that: The catalyst is 4-(dimethylamino)pyridine; the weight ratio of the catalyst to hydroxyethyl methacrylate is 1-5:

100.

5. The ethanol-soluble halogen-free flame retardant spray for cotton fabric according to claim 1, characterized in that: The cross-linking agent is azobisisobutyronitrile; the weight ratio of the cross-linking agent to hydroxyethyl methacrylate is 1 to 5:

100.

6. The ethanol-soluble halogen-free flame retardant spray for cotton fabric according to claim 1, characterized in that: The reaction solvent is ethanol; the volume ratio of the solvent to the flame retardant is 1-100:

1.

7. A method for preparing the ethanol-soluble halogen-free flame retardant spray for cotton fabric according to any one of claims 1 to 6, characterized in that: The method is specifically as follows: Hydroxyethyl methacrylate, sodium vinyl sulfonate, 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate and ethanol are added into a reactor, stirred and mixed evenly under nitrogen protection, and the temperature is raised to 45° C. to obtain a base material; the base material and a cross-linking agent are mixed, and reacted at 60-70° C. for 14-20 hours under nitrogen protection to obtain the base material.

8. The method for preparing the ethanol-soluble halogen-free flame retardant spray for cotton fabric according to claim 7, characterized in that: The preparation operation of the 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate is as follows; Dissolve diphenylphosphinyl chloride in an anhydrous organic solvent, add an excess of an acid-binding agent and a catalyst 4-(dimethylamino)pyridine, then dropwise add dried hydroxyethyl methacrylate under anaerobic conditions, keep the reaction temperature below 20°, react until the reaction is completed as detected, filter out the produced solid by-products, and remove the reaction solvent by low-temperature rotary evaporation to obtain the 2-diphenylphosphoryloxyethyl 2-methylprop-2-enoate.

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