Assistant with surface activity and coupling flame retardant effect and preparation method thereof

Abstract

The invention relates to the field of high polymer materials, and discloses a surface-active coupling flame-retardant auxiliary agent and a preparation method thereof.The preparation method of the auxiliary agent comprises the following steps that 1, octadecylamine and isopropyl alcohol are added into a reactor, then 3-glycidyl ether oxypropyl trimethoxy silane is added, mixing reaction is conducted, and an intermediate M is obtained; 2) adding acrylic acid into the intermediate M, mixing and reacting to obtain an intermediate N; and 3) adding a 3-chloro-2-hydroxy propyl sodium sulfonate aqueous solution into the intermediate N, and carrying out mixing reaction to obtain the surface-active coupling flame-retardant auxiliary agent. The auxiliary agent with the surface-active coupling flame-retardant effect has the structural characteristics of a silane type coupling agent, contains flame-retardant element silicon and sulfonate groups, has surface-active groups sulfonate, carboxylic acid and quaternary ammonium salt, and improves the flame-retardant effect of a material.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to an auxiliary agent with surface active coupled flame retardant effect and a preparation method thereof. Background Art

[0002] In the underground working environment of coal mines, conveyor belts are one of the key transportation equipment, and the material properties directly affect the safety and efficiency of the mine. Although traditional rubber conveyor belts have certain wear resistance and mechanical strength, they still have great deficiencies in fire prevention and flame retardancy. Under high temperature or fire conditions, ordinary rubber materials are easy to burn and produce toxic smoke, posing a serious threat to personnel safety. Therefore, the development of a rubber material with excellent flame retardant properties, especially a conveyor belt material suitable for use in coal mines, has important practical significance and application value.

[0003] In order to improve the flame retardant properties of rubber materials, the existing technology usually achieves this by adding flame retardants. However, simply adding traditional flame retardants often brings some new problems. For example, the compatibility of flame retardants with rubber matrix is ​​poor, which easily leads to the decline of mechanical properties of materials, uneven dispersion of fillers, and complex production processes. In addition, conventional flame retardants have poor stability at high temperatures and are easy to decompose, resulting in a short-lasting flame retardant effect.

[0004] At the same time, other properties of rubber materials, such as mechanical strength, wear resistance and processing performance, cannot be significantly affected by the improvement of flame retardancy. Therefore, the market urgently needs a comprehensive modification additive that can effectively improve the flame retardancy of rubber materials while maintaining or improving their mechanical and processing properties.

[0005] In view of these problems, the present invention proposes an auxiliary agent with surface active coupled flame retardant effect. Summary of the invention

[0006] The present invention is aimed at the research on the preparation process and mechanism of the flame-retardant conveyor belt for underground coal mines. By developing an auxiliary agent with surface active coupling flame retardant effect, which has surface active dispersing effect, surface coupling effect and flame retardant effect, the dispersion performance and compatibility of various components in the flame-retardant conveyor belt for underground coal mines can be effectively solved, the mechanical properties of the material can be improved, and the flame retardant performance can be improved.

[0007] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a surface active coupled flame retardant additive having a simple production process, low production cost, environmental friendliness, excellent dispersibility and mechanical properties, and a preparation method and application thereof, which can be used for the preparation of rubber flame retardant materials and can meet the application requirements of conveyor belts in coal mines.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solutions: The first aspect of the present invention provides a surface active coupled flame retardant additive, the molecular structure of which is: .

[0009] This additive combines the properties of surfactants and silane coupling agents in one molecule through a unique molecular design. Its functions include improving the compatibility of materials, improving the dispersibility of fillers, promoting the mechanical properties of materials, and significantly enhancing their flame retardant effects. Multifunctional groups such as sodium sulfonate groups, siloxane groups, and quaternary ammonium salt groups in the additive catalyze the material into carbon when it is thermally decomposed, improving thermal stability and preventing combustion.

[0010] The second aspect of the present invention provides a method for preparing a surface active coupled flame retardant additive, comprising the following steps: 1) Add octadecylamine and isopropanol into a reactor, and then add 3-glycidyloxypropyltrimethoxysilane, and mix and react to obtain an intermediate M. The structural formula of the intermediate M is: ; 2) Adding acrylic acid to the intermediate M, mixing and reacting, to obtain the intermediate N, the structural formula of the intermediate N is: ; 3) Adding an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate N, mixing and reacting, to obtain a surface active coupled flame retardant additive.

[0011] The third aspect of the present invention provides a rubber flame retardant material for underground conveyor belts in coal mines, which includes the following components in parts by mass: 40 to 60 parts of natural rubber, 40 to 60 parts of butadiene rubber, 40 to 50 parts of reinforcing agent, 4 to 6 parts of activating agent, 0 to 3 parts of stearic acid, 4 to 6 parts of aromatic oil, 1.5 to 3.5 parts of antioxidant, 0.8 to 2.8 parts of accelerator, 20 to 30 parts of chlorinated paraffin 70, 2 to 6 parts of antimony trioxide, 10 to 20 parts of aluminum hydroxide, 0.1 to 0.75 parts of a surface active coupled flame retardant additive and 1 to 4 parts of a vulcanizing agent.

[0012] A fourth aspect of the present invention provides a method for preparing a rubber flame retardant material for a conveyor belt in a coal mine, comprising the following steps: A. Mix 4 to 6 parts of active agent, 2 to 6 parts of antimony trioxide, 10 to 20 parts of aluminum hydroxide and 0.1 to 0.75 parts of surface active coupled flame retardant additive, stir evenly, and dry at 40 to 60°C to obtain component A; B. 40-60 parts of natural rubber and 40-60 parts of butadiene rubber are put into an internal mixer at a rotor speed of 30-35 r / min and a top bolt pressure of 2.5-4.0 bar, and mixed for 20-30 seconds to obtain component B; C. Add component A, 20-30 parts of chlorinated paraffin 70, 0-3 parts of stearic acid, 4-6 parts of aromatic oil, 1.5-3.5 parts of antioxidant and 0.8-2.8 parts of accelerator to component B, and continue mixing for 60-90 seconds to obtain component C; D. Add 40-50 parts of reinforcing agent to component C, continue mixing for 100-120 seconds, control the debonding temperature ≤130℃, debond; further mix on the open mill (cut off twice, turn over three times), then roll down the sheet, pass through the isolation agent tank, and enter the wind room to cool to room temperature to obtain component D; E. After leaving component D for 6 to 8 hours, put it into an internal mixer, add 1 to 4 parts of vulcanizer, set the rotor speed at 20 to 25 r / min, set the top bolt pressure at 2.5 to 4.0 bar, mix for 90 to 120 seconds, control the debonding temperature to ≤95°C, and debond; further mix it on the open mixer and roll it into a sheet, pass it through an isolation agent tank, and then cool it to room temperature in a wind room to obtain a flame retardant rubber material for underground conveyor belts in coal mines.

[0013] In a fifth aspect of the present invention, the present invention provides a use of the surface active coupled flame retardant additive as described in the first aspect in an underground conveyor belt of a coal mine.

[0014] The present invention provides an additive with surface active coupled flame retardant effect and a preparation method thereof. It has the following beneficial effects: 1. The rubber flame retardant material for underground conveyor belts in coal mines prepared by the surface active coupled flame retardant additive of the present invention has excellent mechanical and mechanical properties, as well as flame retardant properties.

[0015] 2. The surface active coupling flame retardant auxiliary agent of the present invention has the structural characteristics of a silane coupling agent, contains flame retardant elements silicon and sulfonate groups, and has surface active groups sulfonate, carboxylic acid and quaternary ammonium salt, thereby improving the flame retardant effect of the material.

[0016] 3. The surface active coupled flame retardant additive and the rubber flame retardant material for underground conveyor belts in coal mines of the present invention have low production costs and simple production processes.

[0017] 4. The production of the surface active coupled flame retardant additive of the present invention does not pollute the environment. The rubber flame retardant material for underground conveyor belts in coal mines is environmentally friendly, has good dispersibility and mechanical properties, and can meet the requirements for underground conveyor belts in coal mines.

[0018] 5. Due to the addition of a surface active coupled flame retardant additive, the mutual dispersibility and coupling of the inorganic and organic components in the rubber flame retardant material for underground conveyor belts in coal mines of the present invention are very strong, so its mechanical properties are very good, further improving the flame retardant properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the process flow for preparing the surface active coupled flame retardant additive of the present invention; Figure 2 This is the infrared spectrum of the surface active coupled flame retardant auxiliary product prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the specification of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Please see attached Figure 1 The embodiment of the present invention provides a surface active coupled flame retardant additive, and the preparation method thereof has the following steps: 1) Add octadecylamine and isopropanol into a reactor, then add 3-glycidyloxypropyltrimethoxysilane, mix and react to obtain an intermediate M. The structural formula of the intermediate M is: ; 2) Add acrylic acid to the intermediate M, mix and react to obtain the intermediate N, the structural formula of the intermediate N is: ; 3) Adding an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate N, mixing and reacting, to obtain a surface active coupled flame retardant additive.

[0023] The reaction equation is as follows: (1) (2) (3) The surface active coupled flame retardant additive prepared by the above steps has the following molecular structure: .

[0024] In some embodiments, the molar ratio of octadecylamine, 3-glycidyloxypropyltrimethoxysilane, acrylic acid, and sodium 3-chloro-2-hydroxypropylsulfonate is 1:(1.0-1.2):(1.0-1.2):(1.0-1.3).

[0025] In some embodiments, the mass ratio of octadecylamine to isopropanol is 1:(1.5-3.5).

[0026] In some embodiments, the mass fraction of sodium 3-chloro-2-hydroxypropyl sulfonate in the sodium 3-chloro-2-hydroxypropyl sulfonate aqueous solution is 27% to 39%.

[0027] In some embodiments, in step 1), during the synthesis of intermediate M, the reaction temperature is 65-80° C. and the reaction time is 3-5 h.

[0028] In some embodiments, in step 2), during the synthesis of intermediate N, the reaction temperature is 65-80° C. and the reaction time is 2-4 h.

[0029] In some embodiments, in step 3), the reaction temperature is 65-80° C., and the reaction time is 4-6 h.

[0030] In some embodiments, the preparation method of the above-mentioned surface active coupled flame retardant additive specifically comprises the following steps: (1) Add octadecylamine and isopropanol to a reactor, then add 3-glycidyloxypropyltrimethoxysilane, heat and stir, and react at 65-80°C for 3-5 hours to obtain an intermediate M; (2) Add acrylic acid to the intermediate M and react at 65-80°C for 2-4 hours to obtain the intermediate N; (3) Add 27% to 39% aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate N and react at 65 to 80° C. for 4 to 6 h to obtain a surface active coupled flame retardant additive.

[0031] The embodiment of the present invention also provides a rubber flame retardant material for a conveyor belt in an underground coal mine, which includes the following components in parts by mass: 40 to 60 parts of natural rubber, 40 to 60 parts of butadiene rubber, 40 to 50 parts of a reinforcing agent, 4 to 6 parts of an active agent, 0 to 3 parts of stearic acid, 4 to 6 parts of aromatic oil, 1.5 to 3.5 parts of an antioxidant, 0.8 to 2.8 parts of an accelerator, 20 to 30 parts of chlorinated paraffin 70, 2 to 6 parts of antimony trioxide, 10 to 20 parts of aluminum hydroxide, 0.1 to 0.75 parts of a surface active coupled flame retardant additive and 1 to 4 parts of a vulcanizing agent.

[0032] In some embodiments, natural rubber is used in combination with a polybutylene rubber polymer material having a highly flexible molecular chain, so that it has good physical and mechanical properties. The natural rubber provides excellent elasticity and tear resistance, while the polybutylene rubber improves the overall wear resistance and aging resistance due to its highly flexible molecular chain.

[0033] In some embodiments, the reinforcing agent is carbon black, model N220, which not only enhances the mechanical properties of the rubber, such as tensile strength and wear resistance, but also improves filler dispersion through its high structure.

[0034] In some embodiments, the active agent is one or both of zinc oxide and magnesium oxide, which increase the crosslinking rate, enhance the vulcanization efficiency, and provide anti-aging properties.

[0035] In some embodiments, stearic acid is used as an external lubricant to improve processing rheology and surface finish.

[0036] In some embodiments, the aromatic oil has good rubber compatibility and can greatly improve the processing properties of the rubber, allowing the filler in the rubber compound to be mixed and dispersed, improving the processing properties of the rubber, enhancing the compatibility of the filler with the rubber matrix, and promoting better dispersion.

[0037] In some embodiments, the antioxidant is one or two of antioxidant 4010 (N-cyclohexyl-N'-phenyl-p-phenylenediamine), antioxidant RD (2,2,4-trimethyl-1,2-dihydroquinoline polymer), and antioxidant 4020 (N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine). These compounds help resist oxidation, thermal aging, and light aging, and extend the service life of the material.

[0038] In some embodiments, the accelerator is one or both of CZ (N-cyclohexyl-2-benzothiazole sulfenamide) and DM (2,2'-dibenzothiazole disulfide), and the two accelerators help control the vulcanization speed and efficiency and improve the physical and mechanical properties of the rubber.

[0039] In some embodiments, chlorinated paraffin 70, aluminum hydroxide, and antimony trioxide are flame retardant fillers, which have a synergistic effect. These materials are used together to provide excellent flame retardant effects. Antimony trioxide and aluminum hydroxide can especially release non-toxic smoke when burning while reducing the heat release rate.

[0040] In some embodiments, the vulcanizing agent is sulfur, which promotes cross-linking between rubber chains to form a stable three-dimensional network structure.

[0041] The additive with surface active coupled flame retardant effect in the present invention integrates the characteristics of surfactant and silane coupling agent. The molecular structure designed by this additive can not only improve the processability and mechanical properties of the material, but also significantly improve the flame retardant properties of the material. The specific functions are as follows: 1. Coupling effect: Siloxane groups and hydroxyl groups: provide strong coupling ability, can effectively combine with rubber matrix and inorganic filler, and enhance the structural integrity of the material.

[0042] 2. Surface activity and dispersibility: Hydrophobic alkyl, sodium sulfonate, carboxyl and quaternary ammonium groups: These groups give the additives excellent surface activity and dispersibility, allowing the additives to act as dispersants and surface modifiers to promote the uniform dispersion of different components in the rubber matrix.

[0043] 3. Catalytic carbonization: Sodium sulfonate group: It acts as a catalyst when the material is thermally decomposed, promoting the carbonization reaction, thereby increasing the thermal stability of the material and improving its flame retardancy.

[0044] The embodiment of the present invention also provides a method for preparing the rubber flame retardant material for a coal mine underground conveyor belt, comprising the following steps: A. Mix 4 to 6 parts of active agent, 2 to 6 parts of antimony trioxide, 10 to 20 parts of aluminum hydroxide and 0.1 to 0.75 parts of surface active coupled flame retardant additive, stir evenly, and dry at 40 to 60°C to obtain component A; B. 40-60 parts of natural rubber and 40-60 parts of butadiene rubber are put into an internal mixer at a rotor speed of 30-35 r / min and a top bolt pressure of 2.5-4.0 bar, and mixed for 20-30 seconds to obtain component B; C. Add component A, 20-30 parts of chlorinated paraffin 70, 0-3 parts of stearic acid, 4-6 parts of aromatic oil, 1.5-3.5 parts of antioxidant and 0.8-2.8 parts of accelerator to component B, and continue mixing for 60-90 seconds to obtain component C; D. Add 40-50 parts of reinforcing agent to component C, continue mixing for 100-120 seconds, control the debonding temperature ≤130℃, debond; further mix on the open mill (cut off twice, turn over three times), then roll down the sheet, pass through the isolation agent tank, and enter the wind room to cool to room temperature to obtain component D; E. After leaving component D for 6 to 8 hours, put it into an internal mixer, add 1 to 4 parts of vulcanizer, set the rotor speed at 20 to 25 r / min, set the top bolt pressure at 2.5 to 4.0 bar, mix for 90 to 120 seconds, control the debonding temperature to ≤95°C, and debond; further mix it on the open mixer and roll it into a sheet, pass it through an isolation agent tank, and then cool it to room temperature in a wind room to obtain a flame retardant rubber material for underground conveyor belts in coal mines.

[0045] The application of this additive significantly improves the compatibility of rubber polymer materials during the preparation process, especially the interaction with components such as reinforcing agents, activators, antioxidants, accelerators, flame retardant fillers and vulcanizers. This improvement not only promotes the mutual dispersion and mixing of these components, but also improves the entire production process, thereby improving the physical and mechanical properties of the finished material.

[0046] The present invention will be further described below in conjunction with the embodiments.

[0047] Embodiment 1: (1) Preparation of surface active coupled flame retardant additives: 1) 269.51 g of octadecylamine was dissolved in 650 g of isopropanol, and 245.8 g of 3-glycidyloxypropyltrimethoxysilane was added, and the mixture was stirred at 75° C. for 4 h to obtain intermediate M; 2) Add 75.0 g of acrylic acid to intermediate M, stir and react at 75°C for 3 h to obtain intermediate N; 3) Add 440 g of water to 220.6 g of sodium 3-chloro-2-hydroxypropyl sulfonate (content 98%) and dissolve to obtain an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate; add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate N, stir and react at 75° C. for 5 h to obtain a surface active coupled flame retardant additive.

[0048] The infrared spectrum of the prepared surface active coupled flame retardant additive (such as Figure 2 Shown): 3361 cm -1 (Peak 1) is the OH stretching vibration peak, 2918 cm -1 (Peak 2) is the asymmetric stretching vibration peak of CH2, 2850 cm -1 (Peak 3) is the symmetric stretching vibration peak of CH2, 1714 cm -1 (Peak 4) is the stretching vibration peak of carboxylic acid C=O, 1467 cm -1 (Peak 5) is the asymmetric bending vibration peak of CH2, 1379 cm -1 (Peak 6) is the symmetrical bending vibration peak of CH2, 1197 cm -1 (Peak 7) is the symmetric stretching vibration peak of the sulfonic acid group S=O, 1041 cm -1 (Peak 8) is the asymmetric stretching vibration peak of the sulfonic acid group S=O, 817 cm -1 (Peak 9) is the Si-C stretching vibration peak, 721 cm -1 (Peak 10) is the CH2 in-plane rocking vibration peak, 482 cm -1 (Peak 11) is the Si-O peak.

[0049] Embodiment 2: (1) Composition of rubber flame retardant materials for underground conveyor belts in coal mines: The invention comprises the following components in parts by mass: 50 parts of natural rubber (No. 1), 50 parts of butadiene rubber (model BR9000), 45 parts of reinforcing agent (carbon black N220), 5 parts of activator (zinc oxide), 2 parts of stearic acid, 5 parts of aromatic oil, 1.5 parts of antioxidant RD, 1.0 parts of antioxidant 4010, 1.3 parts of accelerator CZ, 0.5 parts of accelerator DM, 25 parts of chlorinated paraffin 70, 4 parts of antimony trioxide, 15 parts of aluminum hydroxide (model ATH-8), 0.3 parts of a surface active coupled flame retardant additive (Example 1) and 2 parts of sulfur.

[0050] (2) Preparation method of rubber flame retardant material for underground conveyor belt in coal mines: A. 15 parts of aluminum hydroxide (model ATH-8) and 0.3 parts of a surface active coupled flame retardant additive (Example 1) were mixed, stirred evenly, and dried at 50° C. to obtain component A; B. 50 parts of natural rubber (No. 1) and 50 parts of butadiene rubber (model BR9000) were put into an internal mixer at a rotor speed of 33 r / min and a top bolt pressure of 3.5 bar, and mixed for 25 seconds to obtain component B; C. Add component A, 25 parts of chlorinated paraffin 70, 5 parts of activator (zinc oxide), 4 parts of antimony trioxide, 2 parts of stearic acid, 5 parts of aromatic oil, 1.5 parts of antioxidant RD, 1.0 parts of antioxidant 4010, 1.3 parts of accelerator CZ and 0.5 parts of accelerator DM to component B, and continue mixing for 80 seconds to obtain component C; D. Add 45 parts of reinforcing agent (carbon black N220) to component C, continue mixing for 110s, control the debonding temperature ≤130℃, debond; further mix on the open mill (cut off twice, turn over three times), then calender the sheet, pass through the release agent tank and enter the air room to cool to room temperature to obtain component D; E. After the D component is left for 8 hours, it is put into an internal mixer, 2 parts of sulfur is added, the rotor speed is 22r / min, the top bolt pressure is 3.5bar, and the mixing is performed for 110s. The discharge temperature is controlled to be ≤95℃, and the rubber is discharged; after further mixing in the open mixer, the sheet is calendered, and after passing through the isolation agent tank, it enters the wind room to be cooled to room temperature, and the rubber flame retardant material for underground conveyor belts in coal mines is obtained.

[0051] The rubber flame retardant material for the coal mine underground conveyor belt in step E is made into a standard test sample, and various properties are measured according to MT / T914-2019 and GB / T10707-2008.

[0052] Embodiment 3: The same as Example 2, except that 0.3 parts of the surface active coupled flame retardant additive is replaced by 0.75 parts of the surface active coupled flame retardant additive.

[0053] Embodiment 4: The same as Example 2, except that 0.3 parts of the surface active coupled flame retardant additive is replaced by 1.5 parts of the surface active coupled flame retardant additive.

[0054] Embodiment 5: (1) Composition of rubber flame retardant materials for underground conveyor belts in coal mines: The invention comprises the following components in parts by mass: 50 parts of natural rubber (No. 1), 50 parts of butadiene rubber (model BR9000), 45 parts of reinforcing agent (carbon black N220), 5 parts of activator (zinc oxide), 0 parts of stearic acid, 5 parts of aromatic oil, 1.5 parts of antioxidant RD, 1.0 parts of antioxidant 4010, 1.3 parts of accelerator CZ, 0.5 parts of accelerator DM, 25 parts of chlorinated paraffin 70, 4 parts of antimony trioxide, 15 parts of aluminum hydroxide (model ATH-8), 0.24 parts of a surface active coupled flame retardant additive (Example 1) and 2 parts of sulfur.

[0055] (2) Preparation method of rubber flame retardant material for underground conveyor belt in coal mines: A. Mix 5 parts of active agent (zinc oxide), 4 parts of antimony trioxide, 15 parts of aluminum hydroxide (model ATH-8) and 0.24 parts of surface active coupled flame retardant additive (Example 1), stir evenly, and dry at 50°C to obtain component A; B. 50 parts of natural rubber (No. 1) and 50 parts of butadiene rubber (model BR9000) were put into an internal mixer at a rotor speed of 33 r / min and a top bolt pressure of 3.5 bar, and mixed for 25 seconds to obtain component B; C. Add component A, 25 parts of chlorinated paraffin 70, 0 parts of stearic acid, 5 parts of aromatic oil, 1.5 parts of antioxidant RD, 1.0 parts of antioxidant 4010, 1.3 parts of accelerator CZ and 0.5 parts of accelerator DM to component B, and continue mixing for 80 seconds to obtain component C; D. Add 45 parts of reinforcing agent (carbon black N220) to component C, continue mixing for 110s, control the debonding temperature ≤130℃, debond; further mix on the open mill (cut off twice, turn over three times), then calender the sheet, pass through the release agent tank and enter the air room to cool to room temperature to obtain component D; E. After the D component is left for 8 hours, it is put into an internal mixer, 2 parts of sulfur is added, the rotor speed is 22r / min, the top bolt pressure is 3.5bar, and the mixing is performed for 110s. The discharge temperature is controlled to be ≤95℃, and the rubber is discharged; after further mixing in the open mixer, the sheet is calendered, and after passing through the isolation agent tank, it enters the wind room to be cooled to room temperature, and the rubber flame retardant material for underground conveyor belts in coal mines is obtained.

[0056] The rubber flame retardant material for the coal mine underground conveyor belt in step E is made into a standard test sample, and various properties are measured according to MT / T914-2019 and GB / T10707-2008.

[0057] Embodiment 6: The same as Example 5, except that 0.24 parts of the surface active coupled flame retardant additive is replaced by 0.72 parts of the surface active coupled flame retardant additive.

[0058] Comparative Example 1 The same as Example 2, except that 0.3 parts of the surface active coupled flame retardant auxiliary agent is not added.

[0059] Comparative Example 2 The same as Example 5, except that 0.24 parts of the surface active coupled flame retardant auxiliary agent is not added.

[0060] Experimental Example 1: Table 1 shows the performance test results of the flame retardant materials prepared in Examples 2 to 4 and Comparative Example 1. It can be seen that the various properties of Examples 2 to 4 are good and can meet the standard requirements. It can be further concluded that the addition of the surfactant coupled flame retardant additive in Examples 2 to 4 significantly improves the tensile strength and elongation. In addition, since the amount of the surfactant coupled flame retardant additive added in Example 4 is too large, a single index will be reduced (such as elongation).

[0061] Table 1 Experimental data

[0062] Experimental Example 2: Table 2 shows the performance test results of the flame retardant materials prepared in Examples 5-6 and Comparative Example 2. It can be seen that the various properties of Examples 5-6 are good and can meet the standard requirements. It can be further concluded that the addition of a surface active coupled flame retardant additive to Examples 5-6 significantly improves the tensile strength and elongation. The oxygen index is also improved. Since the material's own catalytic carbonization is promoted during combustion, the mean and maximum values ​​in the alcohol burner flame combustion test have been significantly reduced. The shorter the time, the better the flame retardant performance.

[0063] Table 2 Experimental data

[0064] It can be concluded that: compared with Comparative Example 2, the addition of a surface-active coupled flame-retardant additive significantly improves the physical and mechanical properties and flame-retardant properties of the rubber flame-retardant material for underground conveyor belts in coal mines; and the amount added is very small, that is, adding 0.1 to 0.75 parts can achieve very good technical effects; the added surface-active coupled flame-retardant additive also acts as a catalyst, which promotes the carbonization of the material itself when it is thermally decomposed, thereby improving the flame-retardant properties of the material.

[0065] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A surface active coupled flame retardant additive, characterized in that: The molecular structural formula of the auxiliary agent is:

2. The method for preparing a surface active coupled flame retardant additive according to claim 1, characterized in that: The following steps are involved: 1) Add octadecylamine and isopropanol into a reactor, and then add 3-glycidyloxypropyltrimethoxysilane, and mix and react to obtain an intermediate M. The structural formula of the intermediate M is: ； 2) Adding acrylic acid to the intermediate M, mixing and reacting, to obtain the intermediate N, the structural formula of the intermediate N is: ； 3) Adding an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate N, mixing and reacting, to obtain a surface active coupled flame retardant additive.

3. The preparation method according to claim 2, characterized in that: The molar ratio of octadecylamine, 3-glycidyloxypropyltrimethoxysilane, acrylic acid and sodium 3-chloro-2-hydroxypropylsulfonate is 1:(1.0-1.2):(1.0-1.2):(1.0-1.3).

4. The preparation method according to claim 2, characterized in that: The mass ratio of the octadecylamine to the isopropanol is 1:(1.5-3.5).

5. The preparation method according to claim 2, characterized in that: The mass fraction of sodium 3-chloro-2-hydroxypropyl sulfonate in the sodium 3-chloro-2-hydroxypropyl sulfonate aqueous solution is 27% to 39%.

6. The preparation method according to claim 2, characterized in that: In the step 1), during the synthesis of the intermediate M, the reaction temperature is 65-80°C and the reaction time is 3-5 h; In the step 2), during the synthesis of intermediate N, the reaction temperature is 65-80°C and the reaction time is 2-4 h; In the step 3), the reaction temperature is 65-80° C. and the reaction time is 4-6 h.

7. The use of the surface active coupled flame retardant additive in underground conveyor belts of coal mines according to claim 1, characterized in that: The rubber flame retardant material for the underground conveyor belt of the coal mine includes the following components in parts by mass: 40 to 60 parts of natural rubber, 40 to 60 parts of butadiene rubber, 40 to 50 parts of reinforcing agent, 4 to 6 parts of activating agent, 0 to 3 parts of stearic acid, 4 to 6 parts of aromatic oil, 1.5 to 3.5 parts of antioxidant, 0.8 to 2.8 parts of accelerator, 20 to 30 parts of chlorinated paraffin 70, 2 to 6 parts of antimony trioxide, 10 to 20 parts of aluminum hydroxide, 0.1 to 0.75 parts of a surface active coupled flame retardant additive and 1 to 4 parts of a vulcanizing agent.

8. The use according to claim 7, characterized in that: The reinforcing agent is carbon black; The active agent is one or both of zinc oxide and magnesium oxide; The antioxidant is one or two of antioxidant 4010 (N-cyclohexyl-N'-phenyl-p-phenylenediamine), antioxidant RD (2,2,4-trimethyl-1,2-dihydroquinoline polymer), and antioxidant 4020 (N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine); The accelerator is one or both of CZ (N-cyclohexyl-2-benzothiazole sulfenamide) and DM (2,2'-dibenzothiazole disulfide); The chlorinated paraffin 70, aluminum hydroxide and antimony trioxide are flame retardant fillers; The vulcanizing agent is sulfur.

9. The use according to claim 7, characterized in that: The method for preparing the rubber flame retardant material for the underground conveyor belt of a coal mine comprises the following steps: A. Mix 4 to 6 parts of active agent, 2 to 6 parts of antimony trioxide, 10 to 20 parts of aluminum hydroxide and 0.1 to 0.75 parts of surface active coupled flame retardant additive, stir evenly, and dry at 40 to 60°C to obtain component A; B. 40-60 parts of natural rubber and 40-60 parts of butadiene rubber are put into an internal mixer at a rotor speed of 30-35 r / min and a top bolt pressure of 2.5-4.0 bar, and mixed for 20-30 seconds to obtain component B; C. Add component A, 20-30 parts of chlorinated paraffin 70, 0-3 parts of stearic acid, 4-6 parts of aromatic oil, 1.5-3.5 parts of antioxidant and 0.8-2.8 parts of accelerator to component B, and continue mixing for 60-90 seconds to obtain component C; D. Add 40-50 parts of reinforcing agent to component C, continue mixing for 100-120 seconds, control the debonding temperature ≤130℃, debond; further mix on the open mill and roll down the sheet, pass through the isolation agent tank and enter the wind room to cool to room temperature to obtain component D; E. After leaving component D for 6 to 8 hours, put it into an internal mixer, add 1 to 4 parts of vulcanizer, set the rotor speed at 20 to 25 r / min, set the top bolt pressure at 2.5 to 4.0 bar, mix for 90 to 120 seconds, control the debonding temperature to ≤95°C, and debond; further mix it on the open mixer and roll it into a sheet, pass it through an isolation agent tank, and then cool it to room temperature in a wind room to obtain a flame retardant rubber material for underground conveyor belts in coal mines.

10. The use according to claim 9, characterized in that: The further mixing in the open mixing mill includes two times of cutting off and three times of turning over the rubber.

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