Production process of halogen-free high-flame-retardant cable filling rope

Abstract

The invention relates to the technical field of cable filling rope production, in particular to a production process of a halogen-free high-flame-retardant cable filling rope, and the production process comprises the following steps: S1, pretreatment of a cotton fabric; s2, bleaching the cotton fabric; s3, preparing a flame retardant; s4, flame-retardant finishing is conducted on the cotton fabric through an impregnation method. Diammonium hydrogen phosphate is used as a phosphorus source, urea is used as a nitrogen source, the addition amount of ammonium molybdate is kept to be 6% of the total mass of a system, cotton fibers show the optimal flame retardant property and weight gain balance, under the condition, the weight gain rate of the cotton fibers is only 9-19.2% and is remarkably lower than that of other experimental groups, meanwhile, the limit oxygen index reaches 33-42.5%, and the smoke density is reduced to 39-48%; after the cotton fabric is pretreated by adopting the method, the flame retardant is uniformly distributed on the surface of the fabric, and the surface morphology and the fiber structure of the cotton fabric are not obviously damaged by flame-retardant finishing, so that the flame retardant is uniformly attached.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cable filler rope production, in particular to a production process of halogen-free high-flame-retardant cable filler rope. BACKGROUND

[0002] The combustion of high molecular materials is a complex physical and chemical process, mainly including heating and thermal decomposition. That is, the external heat source makes the material temperature rise to thermal decomposition, so that the main chain of the high molecular material is broken, and volatile products with low molecular weight are generated. At the same time, the combustible gas generated by pyrolysis freely diffuses and mixes with oxygen to form a combustible mixed gas. When the concentration of the mixed gas reaches the explosion limit and the temperature reaches the ignition point, a combustion reaction is initiated, releasing a large amount of heat and light. The heat released by combustion further ignites the material body, forming a "pyrolysis-combustion" process, and finally the flame along the material surface until the combustible material is exhausted or the external heat source is removed, and the combustion reaction gradually stops, leaving a carbonized layer or ash.

[0003] Flame retardants are the core components that give materials fire resistance. To play a role, they need to be closely combined with materials to achieve high-efficiency flame retardation. They can be mainly divided into halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, etc.

[0004] Flame-retardant finishing is a certain treatment of cotton fabric to prevent flame spread and have certain self-extinguishing properties. When the flame is removed, it can stop burning.

[0005] The impregnation method is a relatively mature finishing technology. Cotton fabric is soaked in a flame-retardant solution, dried after a period of time, and then dried. In actual production, this process is convenient to operate and simple in process, and can realize large-scale treatment without complex equipment. Due to its convenience and efficiency, it is widely used in industrial production.

[0006] In the prior art, waste utilization of recycled cotton fabric has become an important way of resource conservation. According to understanding, the annual output of waste textiles is tens of millions of tons, but the utilization rate is not high. Cotton fabric, as a natural fiber fabric, is biodegradable and more environmentally friendly than synthetic fibers. The limiting oxygen index (LOI) of recycled cotton fabric is 18%, which is a flammable material. Flame-retardant treatment of cotton fabric can expand the application scenarios of cotton fabric, and is very suitable for filling in the cable industry. The problem of cotton fabric flame retardant is complex operation, and the flame retardant is not environmentally friendly. Solving the above problems plays an important role in the green development of the cable industry. SUMMARY

[0007] The purpose of the present application is to provide a production process of halogen-free high-flame-retardant cable filler rope to solve the problems raised in the background art.

[0008] To achieve the above object, the present application provides the following technical scheme, a production process of halogen-free high-flame-retardant cable filling rope, steps as follows: S1, pretreatment of cotton fabric The recycled cotton fabric is immersed in hot water at 60-70 DEG C for 90-150 min, and after the immersion is completed, a detergent is used to continue the immersion at 40-50 DEG C for 150-200 min, and a pretreated cotton fabric is obtained. The detergent is prepared by uniformly mixing 8-15 parts of aminocarboxylate, 8-15 parts of gluconic acid, 10-18 parts of disodium ethylenediaminetetraacetate, 10-15 parts of biological protease, 20-25 parts of magnesium silicate, 20-25 parts of sodium percarbonate, 35-50 parts of sodium silicate and 500-1000 parts of water. S2, bleaching of cotton fabric The pretreated cotton fabric is bleached by using a hydrogen peroxide solution with a concentration of 1-5%, and the bleaching time is 30-45 min, and after bleaching, the fabric is washed to neutral and dried, and a bleached cotton fabric is obtained. S3, preparation of flame retardant The flame retardant is prepared by mixing 125-135 parts of diammonium hydrogen phosphate, 5-15 parts of urea, 10 parts of ammonium molybdate and 800-900 parts of deionized water in a mechanical stirring manner for 10 min until a uniform dispersion system is formed. S4, flame-retardant finishing of cotton fabric by immersion method The bleached cotton fabric is soaked in the flame retardant at room temperature for 30-40 min, and then the excess flame retardant in the fabric is removed by a calendering process, and finally the fabric is placed in an oven and baked at 120 DEG C for 90 min to complete the flame-retardant finishing process.

[0009] As a preferred embodiment of the above technical scheme, the recycled cotton fabric is immersed in hot water at 60-70 DEG C for 120 min, and after the immersion is completed, a detergent is used to continue the immersion at 40-50 DEG C for 180 min, and a pretreated cotton fabric is obtained.

[0010] As a preferred embodiment of the above technical scheme, the detergent is prepared by uniformly mixing 8-15 parts of aminocarboxylate, 8-15 parts of gluconic acid, 10-18 parts of disodium ethylenediaminetetraacetate, 10-15 parts of biological protease, 20-25 parts of magnesium silicate, 20-25 parts of sodium percarbonate, 35-50 parts of sodium silicate and 500-1000 parts of water.

[0011] As a preferred embodiment of the above technical scheme, the detergent is prepared by uniformly mixing 8 parts of aminocarboxylate, 8 parts of gluconic acid, 10 parts of disodium ethylenediaminetetraacetate, 10 parts of biological protease, 20 parts of magnesium silicate, 20 parts of sodium percarbonate, 35 parts of sodium silicate and 500 parts of water.

[0012] As the preferred technical solution of the above, the pretreated cotton fabric is bleached by a 3% hydrogen peroxide solution, the bleaching time is 40 min, and the bleached cotton fabric is obtained after being washed to neutral and dried.

[0013] As the preferred technical solution of the above, the flame retardant is prepared by 135 parts of diammonium hydrogen phosphate, 5 parts of urea, 10 parts of ammonium molybdate and 800 parts of deionized water, and is treated by mechanical stirring for 10 minutes until a uniform dispersion system is formed.

[0014] The application provides a production process of a halogen-free high-flame-retardant cable filling rope. 1. Ammonium dihydrogen phosphate is used as a phosphorus source. The phosphate groups contained in the molecular structure of the phosphorus source undergo thermal decomposition reaction at a temperature of 200-300 DEG C to convert into polyphosphoric acid and strong dehydrating agents such as phosphoric anhydride. The dehydrating agents can promote the rapid dehydration and carbonization of the cellulose molecular chain, thereby forming a carbon layer in the condensed phase to insulate heat and oxygen transmission and achieve the flame-retardant effect. 2. Urea is used as a nitrogen source. Urea decomposes at a temperature of 150-250 DEG C to release ammonia and isocyanate. The ammonia plays a role in diluting the oxygen concentration in the gas phase, thereby reducing the content of combustion-supporting gas in the combustion area and inhibiting the continuous combustion reaction. The isocyanate reacts with the hydroxyl groups on the cellulose molecular chain to promote the formation of a dense and stable carbon layer structure. The carbon layer can effectively block the transmission of heat and oxygen to the interior of the fiber and inhibit the release of flammable gas, thereby achieving high-efficiency flame retardation in the condensed phase.

[0015] 3. To solve the problem of a large amount of smoke generated in the combustion process of a single flame retardant, ammonium molybdate (AMO) is introduced as a smoke suppressant. The mechanism of action of AMO covers three aspects of catalytic charring, smoke suppression and synergistic flame retardation. In the aspect of catalytic charring, AMO decomposes to generate MoO3 at a temperature of 300-400 DEG C. MoO3 accelerates the dehydration and carbonization process of cellulose through Lewis acid catalysis. In the aspect of smoke suppression, MoO3 forms nanoscale dispersed metal oxide particles in the condensed phase. These particles effectively capture the carbon black particles in the smoke generated in the combustion process in the carbon layer through physical adsorption and chemical complexation, thereby significantly reducing the smoke density.

[0016] 4. When diammonium hydrogen phosphate is used as a phosphorus source, urea is used as a nitrogen source, and the addition amount of ammonium molybdate is 6% of the total mass of the system, the cotton fiber exhibits the best balance of flame-retardant performance, weight gain and smoke suppression performance. Under this condition, the weight gain rate of the cotton fiber is only 9-19.2%, which is significantly lower than that of other experimental groups, and the limiting oxygen index reaches 33-42.5%, and the smoke density is reduced to 39-48%.

[0017] 5. After the cotton fabric is pretreated using the method of the present invention, the flame retardant exhibits a uniform distribution on the fabric surface. The flame retardant finishing does not cause significant damage to the surface morphology and fiber structure of the cotton fabric, indicating that the flame retardant has achieved uniform adhesion.

[0018] 6. Flame retardant finishing has a certain impact on the mechanical properties of fabrics, but the assessment shows that it is still within the acceptable range for production, proving that the treated cotton fabrics can still meet the actual production needs while maintaining flame retardant properties. Detailed Implementation Example 1

[0019] A production process for halogen-free high flame-retardant cable filler rope includes the following steps: S1. Pretreatment of cotton fabrics Soaking the recycled cotton fabric in hot water at 60-70℃ for 90 minutes can remove surface dust, soften fibers, expand the gaps between cotton fibers, help remove dirt trapped inside the cotton fibers, and also remove some of the water stains, making it easier for subsequent processing. After soaking, continue soaking in detergent at 40-50℃ for 150 minutes to obtain pretreated cotton fabric.

[0020] The detergent, by weight, is prepared by mixing 8 parts aminocarboxylate, 8 parts gluconic acid, 10 parts disodium ethylenediaminetetraacetate, 10 parts biological protease, 20 parts magnesium silicate, 20 parts sodium percarbonate, 35 parts sodium silicate, and 500 parts water evenly. It is used to degrease and clean the surface of recycled cotton fabrics of spinning oils, waxes, or greases; otherwise, these components will hinder the penetration of flame retardants and affect the flame retardant effect.

[0021] S2, Bleaching of cotton fabrics The pretreated cotton fabric was bleached using a 1% hydrogen peroxide solution for 30 minutes. After bleaching, the fabric was thoroughly washed with water until neutral and then dried to obtain the bleached cotton fabric. This process avoids residual oxidant affecting the stability of the flame retardant.

[0022] S3, Preparation of flame retardants The flame retardant is prepared by mechanically stirring 135 parts of diammonium hydrogen phosphate, 5 parts of urea, 10 parts of ammonium molybdate and 800 parts of deionized water for 10 minutes until a uniform dispersion system is formed, based on parts by mass. S4. Flame-retardant finishing of cotton fabrics using the impregnation method. The bleached cotton fabric is immersed in the flame retardant at room temperature for 30-40 minutes. Then, excess flame retardant is removed from the fabric by a rolling process. Finally, the fabric is placed in an oven and baked at a constant temperature of 120°C for 90 minutes to complete the flame retardant finishing process. Example 2

[0023] A production process for halogen-free high flame-retardant cable filler rope includes the following steps: S1. Pretreatment of cotton fabrics Soaking the recycled cotton fabric in hot water at 60-70℃ for 150 minutes can remove surface dust, soften fibers, expand the gaps between cotton fibers, help remove dirt trapped inside the cotton fibers, and also remove some of the water stains, making it easier for subsequent processing. After soaking, continue soaking in detergent at 40-50℃ for 200 minutes to obtain pretreated cotton fabric.

[0024] The detergent, by weight, is prepared by mixing 15 parts aminocarboxylate, 15 parts gluconic acid, 18 parts disodium ethylenediaminetetraacetate, 15 parts biological protease, 25 parts magnesium silicate, 25 parts sodium percarbonate, 50 parts sodium silicate, and 1000 parts water evenly. It is used to degrease and clean the surface of recycled cotton fabrics of spinning oils, waxes, or greases; otherwise, these components will hinder the penetration of flame retardants and affect the flame retardant effect.

[0025] S2, Bleaching of cotton fabrics The pretreated cotton fabric was bleached using a 5% hydrogen peroxide solution for 45 minutes. After bleaching, it was thoroughly washed with water until neutral and then dried to obtain the bleached cotton fabric. This process avoids residual oxidant affecting the stability of the flame retardant.

[0026] S3, Preparation of flame retardants The flame retardant is prepared by mechanically stirring 130 parts of diammonium hydrogen phosphate, 10 parts of urea, 10 parts of ammonium molybdate and 900 parts of deionized water for 10 minutes until a uniform dispersion system is formed, based on parts by mass. S4. Flame-retardant finishing of cotton fabrics using the impregnation method. The bleached cotton fabric is immersed in the flame retardant at room temperature for 30-40 minutes. Then, excess flame retardant is removed from the fabric by a rolling process. Finally, the fabric is placed in an oven and baked at a constant temperature of 120°C for 90 minutes to complete the flame retardant finishing process. Example 3

[0027] A production process for halogen-free high flame-retardant cable filler rope includes the following steps: S1. Pretreatment of cotton fabrics Soaking the recycled cotton fabric in hot water at 60-70℃ for 120 minutes can remove surface dust, soften fibers, expand the gaps between cotton fibers, help remove dirt trapped inside the cotton fibers, and also remove some of the water stains, making it easier for subsequent processing. After soaking, continue soaking in detergent at 40-50℃ for 180 minutes to obtain pretreated cotton fabric.

[0028] The detergent is prepared by mixing 10 parts of aminocarboxylate, 10 parts of gluconic acid, 15 parts of disodium ethylenediaminetetraacetate, 12 parts of biological protease, 22 parts of magnesium silicate, 22 parts of sodium percarbonate, 40 parts of sodium silicate, and 800 parts of water in a uniform manner; it is used for degreasing cleaning of the spinning oil, wax, or grease on the surface of the recovered cotton fabric, otherwise these components will hinder the penetration of the flame retardant and affect the flame retardation effect.

[0029] S2, bleaching of the cotton fabric The pretreated cotton fabric is bleached by using a hydrogen peroxide solution with a concentration of 3%, and the bleaching time is 40 min; after bleaching, the fabric is washed to neutral and then dried to obtain the bleached cotton fabric; the residual oxidant is avoided to affect the stability of the flame retardant.

[0030] S3, preparation of the flame retardant The flame retardant is prepared by mixing 125 parts of diammonium hydrogen phosphate, 15 parts of urea, 10 parts of ammonium molybdate, and 850 parts of deionized water in a mechanical stirring manner for 10 min until a uniform dispersion system is formed; S4, flame retardant finishing of the cotton fabric by the immersion method The bleached cotton fabric is soaked in the flame retardant at room temperature for 30-40 min, and then the excess flame retardant in the fabric is removed by a rolling process, and finally the fabric is placed in an oven and baked at a constant temperature of 120°C for 90 min to complete the flame retardant finishing process.

[0031] Comparative Example 1 In this comparative example, diammonium hydrogen phosphate is not used as the phosphorus source in the flame retardant, but water-soluble ammonium polyphosphate is used as the phosphorus source, i.e., the flame retardant is prepared by mixing 135 parts of water-soluble ammonium polyphosphate, 5 parts of urea, 10 parts of ammonium molybdate, and 800 parts of deionized water, and the other steps are the same.

[0032] Comparative Example 2 In this comparative example, diammonium hydrogen phosphate is not used as the phosphorus source in the flame retardant, but water-soluble ammonium polyphosphate is used as the phosphorus source, i.e., the flame retardant is prepared by mixing 130 parts of water-soluble ammonium polyphosphate, 10 parts of urea, 10 parts of ammonium molybdate, and 900 parts of deionized water, and the other steps are the same.

[0033] Comparative Example 3 In this comparative example, diammonium hydrogen phosphate is not used as the phosphorus source in the flame retardant, but water-soluble ammonium polyphosphate is used as the phosphorus source, i.e., the flame retardant is prepared by mixing 125 parts of water-soluble ammonium polyphosphate, 15 parts of urea, 10 parts of ammonium molybdate, and 850 parts of deionized water, and the other steps are the same.

[0034] Comparative Example 4 The comparative example is compared with example 1, and no diammonium hydrogen phosphate is used as the phosphorus source in the flame retardant, but water-soluble ammonium polyphosphate is used as the phosphorus source, that is, the flame retardant is prepared from 135 parts of ammonium dihydrogen phosphate, 5 parts of urea, 10 parts of ammonium molybdate, and 800 parts of deionized water, and the other method steps are the same.

[0035] Comparative example 5 The comparative example is compared with example 2, and no diammonium hydrogen phosphate is used as the phosphorus source in the flame retardant, but water-soluble ammonium polyphosphate is used as the phosphorus source, that is, the flame retardant is prepared from 130 parts of ammonium dihydrogen phosphate, 10 parts of urea, 10 parts of ammonium molybdate, and 900 parts of deionized water, and the other method steps are the same.

[0036] Comparative example 6 The comparative example is compared with example 3, and no diammonium hydrogen phosphate is used as the phosphorus source in the flame retardant, but water-soluble ammonium polyphosphate is used as the phosphorus source, that is, the flame retardant is prepared from 125 parts of ammonium dihydrogen phosphate, 15 parts of urea, 10 parts of ammonium molybdate, and 850 parts of deionized water, and the other method steps are the same.

[0037] Blank control group 1 Cotton fabric without treatment.

[0038] The halogen-free high-flame-retardant cable filling ropes prepared from the above three examples and six comparative examples are detected, and the performance indicators are shown in Table 1.

[0039] The smoke density (SEA) of the untreated cotton fabric provided in blank control group 1 is taken as 100%, and the untreated cotton fabric provided in blank control group 1 is used as a reference to test the smoke suppression performance of the halogen-free high-flame-retardant cable filling ropes prepared from the above three examples and six comparative examples. According to GB / T16172-2007, the FTT0007 cone calorimeter is used to test under the condition of a radiation power of 50 kW / m 2

[0040] Table 1

[0041] As shown in Table 1, diammonium hydrogen phosphate is used as the phosphorus source, urea is used as the nitrogen source, and the addition amount of ammonium molybdate is kept at 6% of the total mass of the system, and the cotton fiber exhibits the best flame retardant performance, weight gain, and smoke suppression performance balance. Under this condition, the weight gain rate of the cotton fiber is only 9-19.2%, which is significantly lower than that of other experimental groups, and the limiting oxygen index reaches 33-42.5%, and the smoke density is reduced to 39-48%.

[0042] Comparative example 7 The comparative example is compared with example 1, and the only difference is that the cotton fabric pretreatment method of S1 and S2 is not used, but the recovered cotton fabric is washed and dried by using the existing cleaning method, and the other method steps are the same.​

[0043] The flame-retardant finished cotton fabric provided in Example 1 and the cotton fabric provided in Comparative Example 7 were compared, wherein the cotton fabric in Example 1 was treated by the method of the present application, and the flame retardant was evenly distributed on the surface of the fabric. The flame-retardant finishing did not cause obvious damage to the surface morphology and fiber structure of the cotton fabric, indicating that the flame retardant was evenly attached.

[0044] However, in Comparative Example 7, the cotton fabric was not pretreated by S1 and S2, and the flame retardant particles aggregated and accumulated, and the fiber gaps were blocked. The flame retardant could not be evenly distributed on the surface of the fabric, which seriously affected its flame-retardant effect.

[0045] Blank control group 2 Cotton fabric without treatment.

[0046] The mechanical properties of the three filled ropes provided in the three examples and the cotton fabric without treatment in blank control group 2 were analyzed, and the results are shown in Table 2.

[0047] Table 2

[0048] As shown in Table 2, the mechanical property test data showed that the radial and weft tensile strengths of the cotton fabric provided in blank control group 2 were 1840N and 1840N, respectively, and the samples provided in the three examples had different degrees of decrease compared with the cotton fabric provided in blank control group 2. Although this decrease indicates that the flame-retardant finishing has a certain effect on the mechanical properties of the fabric, it is still within the acceptable range of production after evaluation, proving that the treated cotton fabric can maintain the flame-retardant properties while its mechanical properties can still meet the actual production requirements.

[0049] Although embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations can be made thereto without departing from the principles and spirit of the present application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A production process for halogen-free high flame-retardant cable filler rope, characterized in that, The steps are as follows: S1. Pretreatment of cotton fabrics The recycled cotton fabric is immersed in hot water at 60-70℃ for 90-150 minutes. After immersion, it is further immersed in detergent at 40-50℃ for 150-200 minutes to obtain pretreated cotton fabric. S2, Bleaching of cotton fabrics The pretreated cotton fabric was bleached with a 1-5% hydrogen peroxide solution for 30-45 minutes. After bleaching, it was thoroughly washed with water until neutral and then dried to obtain bleached cotton fabric. S3, Preparation of flame retardants The flame retardant is prepared by mechanically stirring 125-135 parts of diammonium hydrogen phosphate, 5-15 parts of urea, 10 parts of ammonium molybdate and 800-900 parts of deionized water for 10 minutes until a uniform dispersion system is formed, based on parts by mass. S4. Flame-retardant finishing of cotton fabrics using the impregnation method. The bleached cotton fabric is immersed in the flame retardant at room temperature for 30-40 minutes. Then, excess flame retardant is removed from the fabric by a rolling process. Finally, the fabric is placed in an oven and baked at a constant temperature of 120°C for 90 minutes to complete the flame retardant finishing process.

2. The production process of a halogen-free high flame-retardant cable filler rope according to claim 1, characterized in that: The recycled cotton fabric is immersed in hot water at 60-70℃ for 120 minutes. After immersion, it is further immersed in detergent at 40-50℃ for 180 minutes to obtain pretreated cotton fabric.

3. The production process of a halogen-free high flame-retardant cable filler rope according to claim 1, characterized in that: The detergent is prepared by mixing 8-15 parts of aminocarboxylate, 8-15 parts of gluconic acid, 10-18 parts of disodium ethylenediaminetetraacetate, 10-15 parts of biological protease, 20-25 parts of magnesium silicate, 20-25 parts of sodium percarbonate, 35-50 parts of sodium silicate, and 500-1000 parts of water evenly by weight.

4. The production process of a halogen-free high flame-retardant cable filler rope according to claim 3, characterized in that: The detergent, by mass, is prepared by mixing 8 parts aminocarboxylate, 8 parts gluconic acid, 10 parts disodium ethylenediaminetetraacetate, 10 parts biological protease, 20 parts magnesium silicate, 20 parts sodium percarbonate, 35 parts sodium silicate, and 500 parts water evenly.

5. The production process of a halogen-free high flame-retardant cable filler rope according to claim 1, characterized in that: The pretreated cotton fabric was bleached using a 3% hydrogen peroxide solution for 40 minutes. After bleaching, the fabric was thoroughly washed with water until neutral and then dried to obtain the bleached cotton fabric.

6. The production process of a halogen-free high flame-retardant cable filler rope according to claim 1, characterized in that: The flame retardant is prepared by mechanically stirring 135 parts of diammonium hydrogen phosphate, 5 parts of urea, 10 parts of ammonium molybdate, and 800 parts of deionized water for 10 minutes until a uniform dispersion system is formed.

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