Flame-retardant vamp material and production process thereof

Abstract

The invention relates to a flame-retardant vamp material and a production process thereof, and the vamp material is prepared from the following raw materials: solution polymerized styrene-butadiene rubber, natural rubber, chlorosulfonated polyethylene, maleic anhydride, methyl vinyl polysiloxane, polytetrafluoroethylene micro powder, triethanolamine, epoxy butyl oleate, magnesium hydroxide, zinc stearate, a vulcanizing agent and a vulcanization accelerator. According to the invention, the solution polymerized styrene-butadiene rubber and the natural rubber are used as basic raw materials, chlorosulfonated polyethylene is added, and triethanolamine is added to cooperate with maleic anhydride as a compatilizer, so that the solution polymerized styrene-butadiene rubber and the natural rubber are uniformly mixed with the chlorosulfonated polyethylene in advance; the polytetrafluoroethylene micro powder and the magnesium hydroxide which are subsequently added as flame retardants can be uniformly dispersed in the mixture, so that the flame retardance and the heat resistance of the prepared vamp material are ensured, and the vamp material can be used for preparing protective shoes.

Description

Technical Field

[0001] The invention belongs to the field of shoe upper material preparation, and particularly relates to a flame-retardant shoe upper material and a production process thereof. Background Art

[0002] There are many types of shoe sole materials, generally categorized as natural and synthetic. Natural sole materials include natural leather, bamboo, and wood, while synthetic sole materials include rubber, PU, ​​and PVC. Common properties of these sole materials include wear resistance, water resistance, good elasticity, easy conformity to the foot shape, and resistance to deformation after shaping. Currently, synthetic sole materials are the most widely used type of shoe material.

[0003] Firefighters need to wear fire-resistant and flame-retardant protective clothing and protective shoes to protect themselves when facing fires. Protective shoes must have fire-resistant and flame-retardant effects, but the flame-retardant effect of existing protective shoes is poor, which cannot effectively protect the lives of firefighters. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a flame retardant shoe upper material and a production process thereof.

[0005] The present invention adopts the following technical solutions:

[0006] A flame-retardant shoe upper material is made from the following raw materials in parts by weight: 40-50 parts of solution-polymerized styrene-butadiene rubber, 20-30 parts of natural rubber, 15-18 parts of chlorosulfonated polyethylene, 5-7 parts of maleic anhydride, 3-5 parts of methyl vinyl polysiloxane, 6-10 parts of polytetrafluoroethylene powder, 3-4 parts of triethanolamine, 1-2 parts of epoxy butyl oleate, 2-6 parts of magnesium hydroxide, 3-5 parts of zinc stearate, 1.8-3.6 parts of a vulcanizing agent, and 2.4-4.2 parts of a vulcanization accelerator.

[0007] Preferably, the vulcanizing agent is insoluble sulfur.

[0008] Preferably, the vulcanization accelerator is composed of zinc dimethyldithiocarbamate, accelerator TMTD, and accelerator M in a mass ratio of 1:0.5-0.6:0.3-0.4.

[0009] A production process for a flame-retardant shoe upper material comprises the following steps:

[0010] Step 1: premixing required weight portions of solution-polymerized styrene-butadiene rubber, natural rubber, chlorosulfonated polyethylene, and maleic anhydride in a high-speed mixer for 10-15 minutes to obtain a premix;

[0011] Step 2: Add the premix prepared in step 1 and other raw materials except the vulcanizing agent and vulcanization accelerator into an internal mixer and mix them, remove the binder at 115-120°C, and place them at room temperature for more than 24 hours;

[0012] Step three, mixing the mixed mixture on a double-roll mill, adding accurately weighed insoluble sulfur and vulcanization accelerator, mixing the materials evenly into sheets, and then putting them into a mold for vulcanization and molding to obtain the flame-retardant shoe upper material.

[0013] Preferably, in step 2, the mixing process specifically includes: adding the premix prepared in step 1 and other raw materials except the vulcanizer and the vulcanization accelerator into the mixer for mixing, mixing and mixing for 10 minutes, adjusting the mixing temperature to 90°C, keeping it for 2 minutes and then turning the material once; when the mixing temperature rises to 96°C, turning the material twice; when the mixing temperature rises to 102°C, turning the material three times; when the mixing temperature rises to 108°C, turning the material four times; when the mixing temperature rises to 115-120°C, turning the material five times, and then mixing for 2 minutes, debinding, and leaving it at room temperature for more than 24 hours.

[0014] Preferably, in step three, the vulcanization temperature is 145-155°C.

[0015] As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following beneficial effects: the present application uses solution-polymerized styrene-butadiene rubber and natural rubber as basic raw materials, adds chlorosulfonated polyethylene, and adds triethanolamine and maleic anhydride as a compatibilizer, so that the solution-polymerized styrene-butadiene rubber and natural rubber are pre-mixed with the chlorosulfonated polyethylene, ensuring that the polytetrafluoroethylene powder and magnesium hydroxide added as flame retardants subsequently can be evenly dispersed in the mixture, ensuring the flame retardancy and heat resistance of the prepared shoe upper material, so that it can be used to prepare protective shoes;

[0016] The raw material composition of the vulcanization accelerator is specifically limited, with zinc dimethyldithiocarbamate as the main raw material, combined with accelerator TMTD and accelerator M, to regulate the cross-linking density of the mixture to form a more stable three-dimensional network structure, delay the performance degradation of the prepared upper material in a high temperature environment, and increase the service life of the upper material. DETAILED DESCRIPTION

[0017] The present invention is further described below through specific embodiments.

[0018] A flame-retardant shoe upper material can be formed into protective shoes through secondary vulcanization with a flame-retardant sole. The material is made of the following raw materials in parts by weight: 40-50 parts of solution-polymerized styrene-butadiene rubber, 20-30 parts of natural rubber, 15-18 parts of chlorosulfonated polyethylene, 5-7 parts of maleic anhydride, 3-5 parts of methylvinylpolysiloxane, 6-10 parts of polytetrafluoroethylene micropowder, 3-4 parts of triethanolamine, 1-2 parts of epoxybutyl oleate, 2-6 parts of magnesium hydroxide, 3-5 parts of zinc stearate, 1.8-3.6 parts of insoluble sulfur, and 2.4-4.2 parts of a vulcanization accelerator. The vulcanization accelerator comprises zinc dimethyldithiocarbamate, accelerator TMTD, and accelerator M in a mass ratio of 1:0.5-0.6:0.3-0.4.

[0019] A production process for a flame-retardant shoe upper material comprises the following steps:

[0020] Step 1: premixing required weight portions of solution-polymerized styrene-butadiene rubber, natural rubber, chlorosulfonated polyethylene, and maleic anhydride in a high-speed mixer for 10-15 minutes to obtain a premix;

[0021] Step 2: Add the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, remove the binder at 115-120° C., and place at room temperature for more than 24 hours. The internal mixing process specifically includes: adding the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, mixing and internal mixing for 10 minutes, adjusting the internal mixing temperature to 90° C., keeping it for 2 minutes, and then turning the material once; when the internal mixing temperature rises to 96° C., turning the material twice; when the internal mixing temperature rises to 102° C., turning the material three times; when the internal mixing temperature rises to 108° C., turning the material four times; when the internal mixing temperature rises to 115-120° C., turning the material five times, and then internal mixing for 2 minutes, removing the binder, and placing at room temperature for more than 24 hours;

[0022] Step three, mixing the mixed mixture on a double-roll mill, adding accurately weighed insoluble sulfur and vulcanization accelerator, mixing the materials evenly into sheets, then putting them into a mold, and vulcanizing and molding them at a temperature of 145-155° C. to obtain the flame-retardant shoe upper material.

[0023] Example 1

[0024] A flame-retardant shoe upper material can be formed into protective shoes through secondary vulcanization with a flame-retardant sole. The material is made of the following raw materials in parts by weight: 40 parts of solution-polymerized styrene-butadiene rubber, 30 parts of natural rubber, 15 parts of chlorosulfonated polyethylene, 7 parts of maleic anhydride, 3 parts of methyl vinyl polysiloxane, 10 parts of polytetrafluoroethylene micropowder, 3 parts of triethanolamine, 2 parts of epoxy butyl oleate, 2 parts of magnesium hydroxide, 5 parts of zinc stearate, 1.8 parts of insoluble sulfur, and 2.4 parts of a vulcanization accelerator. The vulcanization accelerator comprises zinc dimethyldithiocarbamate, accelerator TMTD, and accelerator M in a mass ratio of 1:0.5:0.3.

[0025] A production process for a flame-retardant shoe upper material comprises the following steps:

[0026] Step 1: premixing required weight portions of solution-polymerized styrene-butadiene rubber, natural rubber, chlorosulfonated polyethylene, and maleic anhydride in a high-speed mixer for 10 minutes to obtain a premix;

[0027] Step 2: Add the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, remove the glue at 115° C., and place at room temperature for more than 24 hours. The internal mixing process specifically includes: adding the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, mixing and internal mixing for 10 minutes, adjusting the internal mixing temperature to 90° C., keeping it for 2 minutes, and then turning the material once; when the internal mixing temperature rises to 96° C., turning the material twice; when the internal mixing temperature rises to 102° C., turning the material three times; when the internal mixing temperature rises to 108° C., turning the material four times; when the internal mixing temperature rises to 115° C., turning the material five times, and then internal mixing for 2 minutes, removing the glue, and placing it at room temperature for more than 24 hours;

[0028] Step three, mixing the mixed mixture on a double-roll mill, adding accurately weighed insoluble sulfur and vulcanization accelerator, mixing the materials evenly into sheets, then putting them into a mold, and vulcanizing and molding them at a temperature of 145°C to obtain the flame-retardant shoe upper material.

[0029] Example 2

[0030] A flame-retardant shoe upper material can be formed into protective shoes through secondary vulcanization with a flame-retardant sole. The material is made of the following raw materials in parts by weight: 50 parts of solution-polymerized styrene-butadiene rubber, 20 parts of natural rubber, 18 parts of chlorosulfonated polyethylene, 5 parts of maleic anhydride, 5 parts of methyl vinyl polysiloxane, 6 parts of polytetrafluoroethylene micropowder, 4 parts of triethanolamine, 1 part of epoxy butyl oleate, 6 parts of magnesium hydroxide, 3 parts of zinc stearate, 3.6 parts of insoluble sulfur, and 4.2 parts of a vulcanization accelerator. The vulcanization accelerator comprises zinc dimethyldithiocarbamate, accelerator TMTD, and accelerator M in a mass ratio of 1:0.6:0.4.

[0031] A production process for a flame-retardant shoe upper material comprises the following steps:

[0032] Step 1: premixing required weight portions of solution-polymerized styrene-butadiene rubber, natural rubber, chlorosulfonated polyethylene, and maleic anhydride in a high-speed mixer for 15 minutes to obtain a premix;

[0033] Step 2: Add the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, remove the glue at 120° C., and place at room temperature for more than 24 hours. The internal mixing process specifically includes: adding the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, mixing and internal mixing for 10 minutes, adjusting the internal mixing temperature to 90° C., keeping it for 2 minutes, and then turning the material once; when the internal mixing temperature rises to 96° C., turning the material twice; when the internal mixing temperature rises to 102° C., turning the material three times; when the internal mixing temperature rises to 108° C., turning the material four times; when the internal mixing temperature rises to 120° C., turning the material five times, and then internal mixing for 2 minutes, removing the glue, and placing it at room temperature for more than 24 hours;

[0034] Step three, mixing the mixed mixture on a double-roll mill, adding accurately weighed insoluble sulfur and vulcanization accelerator, mixing the materials evenly into sheets, then putting them into a mold, and vulcanizing and molding them at a temperature of 155°C to obtain the flame-retardant shoe upper material.

[0035] Example 3

[0036] A flame-retardant shoe upper material can be formed into protective shoes through secondary vulcanization with a flame-retardant sole. The material is made of the following raw materials in parts by weight: 45 parts of solution-polymerized styrene-butadiene rubber, 25 parts of natural rubber, 16 parts of chlorosulfonated polyethylene, 6 parts of maleic anhydride, 4 parts of methylvinylpolysiloxane, 8 parts of polytetrafluoroethylene micropowder, 3.5 parts of triethanolamine, 1.5 parts of epoxybutyl oleate, 4 parts of magnesium hydroxide, 4 parts of zinc stearate, 2.7 parts of insoluble sulfur, and 3.5 parts of a vulcanization accelerator. The vulcanization accelerator comprises zinc dimethyldithiocarbamate, accelerator TMTD, and accelerator M in a mass ratio of 1:0.55:0.35.

[0037] A production process for a flame-retardant shoe upper material comprises the following steps:

[0038] Step 1: premixing required weight portions of solution-polymerized styrene-butadiene rubber, natural rubber, chlorosulfonated polyethylene, and maleic anhydride in a high-speed mixer for 12 minutes to obtain a premix;

[0039] Step 2: Add the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, remove the glue at 118° C., and place at room temperature for more than 24 hours. The internal mixing process specifically includes: adding the premix prepared in step 1 and other raw materials except the vulcanizing agent and the vulcanization accelerator to the internal mixer for internal mixing, mixing and internal mixing for 10 minutes, adjusting the internal mixing temperature to 90° C., keeping it for 2 minutes, and then turning the material once; when the internal mixing temperature rises to 96° C., turning the material twice; when the internal mixing temperature rises to 102° C., turning the material three times; when the internal mixing temperature rises to 108° C., turning the material four times; when the internal mixing temperature rises to 118° C., turning the material five times, and then internal mixing for 2 minutes, removing the glue, and placing it at room temperature for more than 24 hours;

[0040] Step three, mixing the mixed mixture on a double-roll mill, adding accurately weighed insoluble sulfur and vulcanization accelerator, mixing the materials evenly into sheets, then putting them into a mold, and vulcanizing and molding them at a temperature of 150° C. to obtain the flame-retardant shoe upper material.

[0041] Comparative Example 1

[0042] The raw material composition and production process are basically the same as those in Example 3, except that chlorosulfonated polyethylene is not added to the raw material composition.

[0043] Comparative Example 2

[0044] The raw material composition and production process are basically the same as those of Implementation 3, with the difference being that polytetrafluoroethylene powder is not added to the raw material composition.

[0045] Comparative Example 3

[0046] The raw material composition and production process are basically the same as those of Implementation 3, with the difference being that the vulcanization accelerator is accelerator TMTD.

[0047] The upper materials prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to corresponding performance tests. Specific results are shown in Table 1. For the heat resistance test, each group of upper materials was placed in an oven at 300°C and 400°C for 30 minutes, then taken out and cooled to test whether each group of upper materials softened or melted. For the flame retardant performance test, quartz sand at 1000°C was poured on the surface of each group of upper materials, left for 3 minutes, and then the combustion of each group of upper materials was observed.

[0048] Table 1 Test data of each embodiment

[0049]

[0050] It can be seen from the above table that the upper material prepared in the present application has excellent flame retardancy and heat resistance, and will not burn after contacting high-temperature objects, and has good safety performance.

[0051] This application uses solution-polymerized styrene-butadiene rubber and natural rubber as basic raw materials, adds chlorosulfonated polyethylene, and adds triethanolamine and maleic anhydride as a compatibilizer, so that the solution-polymerized styrene-butadiene rubber and natural rubber are pre-mixed evenly with the chlorosulfonated polyethylene, ensuring that the polytetrafluoroethylene powder and magnesium hydroxide added subsequently as flame retardants can be evenly dispersed in the mixture, ensuring the flame retardancy and heat resistance of the prepared upper material, so that it can be used to prepare protective shoes.

[0052] The above description is merely a preferred embodiment of the present invention and therefore cannot be used to limit the scope of the present invention. In other words, equivalent changes and modifications made according to the scope of the patent application and the contents of the specification should still fall within the scope of the patent of the present invention.

Claims

1. A flame-retardant shoe upper material, characterized by: The invention is prepared from the following raw materials in parts by weight: 40-50 parts of solution-polymerized styrene-butadiene rubber, 20-30 parts of natural rubber, 15-18 parts of chlorosulfonated polyethylene, 5-7 parts of maleic anhydride, 3-5 parts of methyl vinyl polysiloxane, 6-10 parts of polytetrafluoroethylene powder, 3-4 parts of triethanolamine, 1-2 parts of epoxy butyl oleate, 2-6 parts of magnesium hydroxide, 3-5 parts of zinc stearate, 1.8-3.6 parts of a vulcanizing agent, and 2.4-4.2 parts of a vulcanization accelerator.

2. The flame-retardant shoe upper material according to claim 1, characterized in that: The vulcanizing agent is insoluble sulfur.

3. The flame-retardant shoe upper material according to claim 1, characterized in that: The vulcanization accelerator comprises zinc dimethyldithiocarbamate, accelerator TMTD, and accelerator M in a mass ratio of 1:0.5-0.6:0.3-0.

4.

4. The production process of a flame-retardant shoe upper material according to claim 1, characterized in that: The specific steps include: Step 1: premixing required weight portions of solution-polymerized styrene-butadiene rubber, natural rubber, chlorosulfonated polyethylene, and maleic anhydride in a high-speed mixer for 10-15 minutes to obtain a premix; Step 2: Add the premix prepared in step 1 and other raw materials except the vulcanizing agent and vulcanization accelerator into an internal mixer and mix them, remove the binder at 115-120°C, and place them at room temperature for more than 24 hours; Step three, mixing the mixed mixture on a double-roll mill, adding accurately weighed insoluble sulfur and vulcanization accelerator, mixing the materials evenly into sheets, and then putting them into a mold for vulcanization and molding to obtain the flame-retardant shoe upper material.

5. The production process of a flame-retardant shoe upper material according to claim 4, characterized in that: In step 2, the mixing process specifically includes: adding the premix prepared in step 1 and other raw materials except the vulcanizer and vulcanization accelerator into the mixer for mixing, mixing and mixing for 10 minutes, adjusting the mixing temperature to 90°C, keeping it for 2 minutes and then turning the material once; when the mixing temperature rises to 96°C, turning the material twice; when the mixing temperature rises to 102°C, turning the material three times; when the mixing temperature rises to 108°C, turning the material four times; when the mixing temperature rises to 115-120°C, turning the material five times, and then mixing for 2 minutes, debonding, and leaving it at room temperature for more than 24 hours.

6. The process for producing a flame-retardant shoe upper material according to claim 4, characterized in that: In step 3, the vulcanization temperature is 145-155°C.

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