Marine breathing mask body rubber compound and application thereof

Abstract

The invention relates to the technical field of rubber compounds, in particular to a marine breathing mask body rubber compound and application thereof. The invention aims to provide a rubber compound which is high in vulcanization efficiency, high in tear resistance, aging-resistant and not easy to deform, and meets the scene use requirements of masks. The rubber compound is prepared from the following raw materials in parts by weight: 60 parts of brominated butyl rubber, 40 parts of natural rubber, 8 to 12 parts of zinc oxide (indirect method), 6.4 to 9.6 parts of magnesium oxide, 0.5 to 2.5 parts of accelerant PX, 0.5 to 2.5 parts of industrial stearic acid, 1.5 to 3 parts of anti-aging agent 264, 1.5 to 3 parts of anti-aging agent MB, 1.5 to 3 parts of semi-refined paraffin, 2 to 5 parts of dioctyl sebacate, 20 to 50 parts of medium super wear-resistant furnace carbon black and 5 to 8 parts of high wear-resistant furnace carbon black. The mask prepared according to the formula has the characteristics of good air tightness, high vulcanization rate, high tearing strength, aging resistance and deformation resistance.

Description

Technical Field

[0001] The invention relates to the technical field of rubber mixes, and in particular to a rubber mix for a marine breathing mask body and application thereof. Background Art

[0002] When a submarine is performing a mission, if a fire is caused by an accident, it will cause the internal wires and cables, oil, internal decoration, thermal insulation and other non-metallic materials of the submarine to burn, which will quickly consume the oxygen in the cabin and release a large amount of toxic and harmful substances, causing suffocation, poisoning and even death of the crew. In this case, an air-supplied breathing device (breathing mask device) is needed to connect the quick connector to the compressed air source, which can not only isolate toxic and harmful substances, but also provide the crew with the air needed to sustain life, and win precious time for the crew to escape or wait for rescue. The mask body, as the largest unit of the breathing mask, undertakes the important task of facial skin protection. In the research of breathing mask materials, the research of mask body materials occupies a core position. In the mask production process, the production of mask body materials can determine the appearance and performance of the final product of the breathing mask. The main rubber type of the mask body material needs to have excellent air tightness, tear resistance, deformation resistance, aging resistance and fast vulcanization rate. The main rubber types of the cover body in general rubber are generally butyl rubber and natural rubber. Butyl rubber has good air tightness and strong tear resistance, but poor processing performance, such as slow vulcanization, poor adhesion, low solubility in common compounding agents, and poor mixing operability; natural rubber has strong tear resistance and deformation resistance, but poor air tightness. At the same time, because natural rubber is a diene rubber, chain olefins are easy to react with oxygen, peroxides, ultraviolet rays and free radicals, and are not resistant to aging. However, in view of the above situation, it is urgent to design and develop a mixed rubber formula that can not only meet the performance requirements of the cover body, but also have the characteristics of fast vulcanization rate and convenient production operation. Summary of the invention

[0003] In order to solve at least one of the above problems, the present application provides a cover body rubber compound in a first aspect, comprising brominated butyl rubber, natural rubber, zinc oxide, magnesium oxide, an accelerator, stearic acid, an antioxidant, a softener, and a reinforcing agent.

[0004] Among them, the accelerator is PX.

[0005] According to a specific implementation plan of the present invention, the cover body compound rubber prepared by the inventor adopts a vulcanization system of ZnO+MgO+PX, and its tear strength, permanent deformation resistance, and 300% elongation strength are better than other systems. Moreover, because the ZnO+MgO+PX vulcanization system is a sulfur-free vulcanization, the vulcanization efficiency is relatively high and the product's aging resistance is relatively excellent.

[0006] According to a specific embodiment of the present invention, the cover body rubber compound includes, by weight: 60 parts of brominated butyl rubber, 40 parts of natural rubber, 8-12 parts of zinc oxide, 6.4-9.6 parts of magnesium oxide, 0.5-2.5 parts of accelerator, 0.5-2.5 parts of stearic acid, 3-6 parts of antioxidant, 3-8 parts of softener, and 25-40 parts of reinforcing agent.

[0007] According to a specific embodiment of the present invention, the antioxidant includes antioxidant 264 and antioxidant MB, wherein antioxidant 264 accounts for 1-3 parts and antioxidant MB accounts for 1-3 parts.

[0008] According to a specific embodiment of the present invention, the softener comprises dioctyl sebacate and paraffin oil, wherein the paraffin oil accounts for 1-4 parts and the dioctyl sebacate accounts for 2-6 parts.

[0009] According to a specific embodiment of the present invention, the reinforcing agent is carbon black.

[0010] According to a specific embodiment of the present invention, the carbon black includes medium-super wear-resistant furnace carbon black and high wear-resistant furnace carbon black, wherein the medium-super wear-resistant carbon black accounts for 25-30 parts and the high wear-resistant carbon black accounts for 1-10 parts.

[0011] According to a more specific embodiment of the present invention, the present invention provides a cover body rubber compound, which includes, by mass, 60 parts of chlorinated butyl rubber, 40 parts of natural rubber, 10 parts of zinc oxide (indirect method), 8 parts of magnesium oxide, 1.5 parts of accelerator PX, 1.5 parts of industrial stearic acid, 2 parts of antioxidant 264, 2 parts of antioxidant MB, 2 parts of semi-refined paraffin, 3 parts of dioctyl sebacate, 30 parts of medium super wear-resistant furnace black, and 7 parts of high wear-resistant furnace black.

[0012] The second aspect of the present invention provides the use of the mask body compound described in the first aspect in the preparation of a marine breathing mask.

[0013] According to a specific embodiment of the present invention, the gas mask prepared with the mask body compound provided by the present invention has better tear resistance, resistance to permanent deformation, 300% tensile strength and aging resistance than other systems.

[0014] A third aspect of the present invention provides a method for preparing a cover body rubber mix, comprising the following steps:

[0015] S1. Adjust the roller temperature of the mixing mill to 50-55°C for the front roller and 45-50°C for the rear roller;

[0016] S2. Adjust the roller distance to 1.0-1.5 mm, add brominated butyl rubber and natural rubber into the open mill, and plasticize and press for 10-15 minutes;

[0017] S3, add antioxidant 264, antioxidant MB and semi-paraffin oil into the open mill, and continue mixing for 5 to 10 minutes;

[0018] S4, adjust the roller distance to 1.5-3.0 mm, add medium-super wear-resistant furnace carbon black, high wear-resistant furnace carbon black, stearic acid, and dioctyl sebacate into the mixing mill, and continue mixing for 15-20 minutes;

[0019] S5. Adjust the roller distance to 3.0-4.0 mm, add medium-super wear-resistant furnace carbon black, high wear-resistant furnace carbon black, stearic acid and dioctyl sebacate into the mixing mill, and continue mixing for 15-20 minutes;

[0020] S6, mix the rubber material for 10 to 15 minutes before unloading;

[0021] S7, adjust the calender roller distance to 1.0-1.5mm, and the roller temperature to 30-40℃;

[0022] S8. Add zinc oxide, magnesium oxide, accelerator PX and mixed rubber into the calender, mix them evenly, and cut them into sheets after mixing for 8 to 10 minutes. After cutting, isolate the sheets with pads and leave them for 4 to 168 hours to obtain the mixed rubber for the cover body.

[0023] According to a specific embodiment of the present invention, the cover body rubber compound contains, by weight: 60 parts of brominated butyl rubber, 40 parts of natural rubber, 8-12 parts of zinc oxide, 6.4-9.6 parts of magnesium oxide, 0.5-2.5 parts of accelerator PX, 0.5-2.5 parts of stearic acid, 1.5-3 parts of antioxidant 264, 1.5-3 parts of antioxidant MB, 1.5-3 parts of paraffin oil, 2-5 parts of dioctyl sebacate, 20-50 parts of medium-super wear-resistant furnace black, and 5-8 parts of high wear-resistant furnace black.

[0024] According to a more specific embodiment of the present invention, the cover body rubber compound contains, by weight: 60 parts of chlorinated butyl rubber, 40 parts of natural rubber, 10 parts of zinc oxide (indirect method), 8 parts of magnesium oxide, 1.5 parts of accelerator PX, 1.5 parts of industrial stearic acid, 2 parts of antioxidant 264, 2 parts of antioxidant MB, 2 parts of semi-refined paraffin, 3 parts of dioctyl sebacate, 30 parts of medium super wear-resistant furnace black, and 7 parts of high wear-resistant furnace black.

[0025] The fourth aspect of the present invention provides a gas mask, comprising the mask body compound rubber described in the first aspect. DETAILED DESCRIPTION

[0026] Embodiments of the present invention are described in detail below. The examples of the embodiments are intended to explain the present invention but are not to be construed as limiting the present invention.

[0027] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. Further, in the description of the present invention, unless otherwise specified, the meaning of "plurality" is two or more.

[0028] In this document, the terms “contain”, “include” or “comprise” are open expressions, that is, they include the contents specified in the present invention but do not exclude other contents.

[0029] As used herein, the terms "optionally", "optional" or "optionally" generally mean that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0030] In this article, the term "high abrasion furnace black" (HAF) is the most commonly used type of hard carbon black, produced by the oil furnace method, with a particle size of 26 to 30 nm. The specific surface area is 80 to 110 m2 / g. The oxygen content is 0.5% to 1.0%. The hydrogen content is 0.27% to 0.34%. The density is about 1.8g / cm3. There are high structure, standard structure and low structure in terms of structure. The tensile strength, tear strength, wear resistance and aging properties given to rubber products are second only to medium and super wear-resistant carbon black. It can be used in tire treads to improve wear resistance and puncture resistance.

[0031] In this article, the term "medium-super wear-resistant carbon black" is a main type of hard carbon black, produced by the oil furnace method, with a particle size of 20-25nm. From the structural point of view, it can be divided into high-structure, standard-structure and low-structure derivatives.

[0032] The object of the present invention is to provide a cover body mixed rubber material which can meet the performance requirements of the cover body and has a fast vulcanization rate and is easy to produce and operate.

[0033] The present invention is achieved through the following scheme:

[0034] A cover body mixed rubber material, in parts by weight, includes 60 parts of brominated butyl rubber, 40 parts of natural rubber, 8-12 parts of zinc oxide, 6.4-9.6 parts of magnesium oxide, 0.5-2.5 parts of accelerator, 0.5-2.5 parts of stearic acid, 3-6 parts of antioxidant, 3-8 parts of softener, and 25-40 parts of reinforcing agent. The preparation steps are as follows:

[0035] S1. Adjust the roller temperature of the mixing mill to 50-55°C for the front roller and 45-50°C for the rear roller;

[0036] S2. Adjust the roller distance to 1.0-1.5 mm, add the weighed brominated butyl rubber and natural rubber into the open mill, and plasticize and press for 10-15 minutes;

[0037] S3. Add the weighed antioxidant 264, antioxidant MB and semi-paraffin oil into the open mill and continue mixing for 5 to 10 minutes;

[0038] S4, adjust the roller distance to 1.5-3.0 mm, add 1 / 2 medium-super wear-resistant furnace carbon black, 1 / 2 high wear-resistant furnace carbon black, 1 / 2 stearic acid, and 1 / 2 dioctyl sebacate into the mixing mill, and continue mixing for 15-20 minutes;

[0039] S5. Adjust the roller distance to 3.0-4.0 mm, add 1 / 2 medium-super wear-resistant furnace carbon black, 1 / 2 high wear-resistant furnace carbon black, 1 / 2 stearic acid, and 1 / 2 dioctyl sebacate into the mixing mill, and continue mixing for 15-20 minutes;

[0040] S6, mix the rubber (triangle bag or eight knives) for 10 to 15 minutes before unloading;

[0041] S7. Adjust the calender roller distance to 1.0-1.5 mm and the roller temperature to 30-40°C.

[0042] S8. Add the weighed zinc oxide, magnesium oxide, accelerator PX and mixed rubber into the calender, mix them evenly with eight knives, and mix for 8 to 10 minutes before unrolling. After unrolling, isolate the film with a pad. To prevent the mixed rubber from self-sulfurization, the film needs to be placed for 4 hours before use, but not more than 7 days.

[0043] On the one hand, the present invention selects the rubber type: halogenated butyl rubber and natural rubber are blended to improve the vulcanization rate, increase the adhesion and solubility of common compounding agents, and improve the mixing operation. Halogenated butyl rubber is generally divided into two types: chlorobutyl and brominated butyl. Because the bromine element is more active than the chlorine element, the vulcanization rate is relatively fast, and the bromine element has a low intrinsic purity and is relatively stable when stored in a suitable environment, brominated butyl rubber is used as the blended rubber material of the cover body.

[0044] On the other hand, the present invention designs the vulcanization system: vulcanization refers to the chemical change process in which intersecting linear macromolecular chains form a three-dimensional spatial network structure through chemical cross-linking. The cross-linking degree of the vulcanized rubber has an important influence on the physical properties of the vulcanized rubber. Considering the performance of the mask and the characteristics of butyl rubber, the vulcanization system design should be carried out around the following points:

[0045] a) Increase the vulcanization rate of the rubber compound while avoiding scorching;

[0046] b) Choose a vulcanization system with low permanent deformation;

[0047] c) Choose a vulcanization system that can increase the modulus by 300%;

[0048] d) Select a vulcanization system with excellent tear resistance;

[0049] e) Choose a vulcanization system with strong aging resistance.

[0050] The main reagents and reagent acquisition sources involved in the present invention are shown in Table 1.

[0051] Table 1

[0052]

[0053]

[0054] In the present application, the tear strength, elongation at break and permanent deformation are determined according to GB / T528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber; the Shore hardness is determined according to GB / T531.1-2008 Test method for indentation hardness of vulcanized rubber or thermoplastic rubber Part 1: Shore hardness method (Shore hardness); the tear strength is determined according to GB / T529-2008 Determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser-shaped, right-angled and crescent-shaped specimens); the anti-mildew ability is determined according to GJB151.10A-2009 Laboratory environmental test methods for military equipment Part 10: Mildew test; hot air aging is determined according to GB / T 3512-2014 Hot air accelerated aging and heat resistance test for vulcanized rubber or thermoplastic rubber; 300% tensile strength (MPa) is determined according to GB / T528-2009 Determination standard of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber.

[0055] It should be noted that the reagents and consumables involved in the present invention can be obtained through conventional purchase, and the asphalts of different penetration degrees of the present invention can also be obtained by those skilled in the art through conventional means. The technical scheme in the embodiments of the present invention will be clearly and completely described below in combination with 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.

[0056] Example 1

[0057] This embodiment provides a cover film, and the specific preparation method is as follows:

[0058] 1) Mixing:

[0059] S1. Adjust the roller temperature of the mixing mill to 50-55°C for the front roller and 45-50°C for the rear roller;

[0060] S2. Adjust the roller distance to 1.0-1.5 mm, add the weighed 30 kg of brominated butyl rubber and 20 kg of natural rubber into the open mill, and plasticize and press for 10-15 minutes;

[0061] S3, add weighed 1kg antioxidant 264, 1kg antioxidant MB, and 1kg semi-paraffin oil into the open mill, and continue mixing for 5 to 10 minutes;

[0062] S4, adjust the roller distance to 1.5-3.0 mm, add 7.5 kg of medium-super wear-resistant furnace carbon black, 1.75 kg of high wear-resistant furnace carbon black, 0.35 kg of stearic acid, and 0.75 kg of dioctyl sebacate into the open mill, and continue mixing for 15-20 min;

[0063] S5. Adjust the roller distance to 3.0-4.0 mm, add 7.5 kg of medium-super wear-resistant furnace carbon black, 1.75 kg of high wear-resistant furnace carbon black, 0.35 kg of stearic acid, and 0.75 kg of dioctyl sebacate into the mixing mill, and continue mixing for 15-20 min;

[0064] S6, mix the rubber materials (triangle bag or eight knives) for 10 to 15 minutes and then unload to obtain BIIR / NR blended rubber;

[0065] 2) Film output:

[0066] S1. Adjust the calender roller distance to 1.0-1.5mm and the roller temperature to 30-40℃.

[0067] S2. Add the weighed 5kg zinc oxide, 4kg magnesium oxide, 0.75kg accelerator PX and BIIR / NR blended rubber to the calender, mix evenly with eight knives, and mix for 8 to 10 minutes before unrolling. After unrolling, isolate the film with a pad to obtain the cover body mixed rubber. To prevent the mixed rubber from self-sulfurization, the film needs to be placed for 4 hours before use, but not more than 7 days.

[0068] The vulcanization system was designed and tested. SP1045+ZnO+ZnCl2·2H2O, ZnO+MgO+PX, S (sulfur)+ZnO+TMTD, S (sulfur)+accelerator DZ+accelerator M were selected and mixed with other compounding agents according to the commonly used dosage. The component ratios of each group are as follows:

[0069] 1) BIIR / NR blended rubber: phenolic resin SP1045: zinc oxide: ZnCl2·2H2O=100:10:2.5:1

[0070] 2) BIIR / NR blended rubber: zinc oxide: magnesium oxide: accelerator PX = 100:10:8:0.5

[0071] 3) BIIR / NR blended rubber: sulfur: zinc oxide: accelerator TMTD = 100: 2.5: 1: 0.5

[0072] 4) BIIR / NR blended rubber: sulfur: accelerator DZ: accelerator M = 100:1.5:1:1.

[0073] Among them, 1) is a phenolic resin vulcanization system, SP1045 resin can form stable -C-C- and -C-O-C- crosslinking bonds, and has good low permanent deformation. The activator ZnCl2·2H2O can increase the vulcanization rate and improve the performance of the rubber compound; 2) is a metal oxide vulcanization system, zinc oxide is used as a vulcanizing agent to make the rubber compound have good heat resistance and ensure the flatness of the vulcanization stage, magnesium oxide improves the anti-scorching property of the rubber compound, increases the storage performance and plasticity of the rubber compound, and the accelerator PX can increase the vulcanization rate; 3) and 4) are sulfur vulcanization systems, zinc oxide and accelerator TMTD are used in 3), the vulcanization speed is faster and the scorch time is shorter; accelerators DZ and M are used in 4), the vulcanization speed is relatively fast, the vulcanization curve has good flatness, the vulcanization induction period is long, and the anti-scorch effect is good.

[0074] The inventors of the present application set up the above four vulcanization systems, combined with BIIR / NR blended rubber, and tested the physical and mechanical properties of the prepared films. The test results are shown in Table 2.

[0075] Table 2 Physical and mechanical properties of films with four curing system formulations

[0076]

[0077] From Table 2, we can see that the second vulcanization system uses ZnO+MgO+PX, and is combined with BIIR / NR blended rubber. Its tear strength, permanent deformation, and 300% elongation strength are better than other systems. Because the ZnO+MgO+PX vulcanization system is sulfur-free vulcanization, the vulcanization efficiency is relatively high and the product's aging resistance is relatively excellent.

[0078] The inventors further adjusted the ratio of accelerator PX in the second vulcanization system BIIR / NR blended rubber: accelerator ZnO: accelerator MgO: accelerator PX = 100:10:8:0.5, and obtained the formula ratio with the best performance by testing the physical and mechanical properties of the film, as shown in Table 3.

[0079] Table 3 Physical and mechanical properties of films with different PX ratios

[0080]

[0081] It can be seen from Table 3 that when the proportion of PX is 1.5 parts, that is, when ZnO:MgO:promoter PX=10:8:1.5, its tear strength, permanent deformation, and 300% tensile strength are relatively excellent, and the film has good mechanical properties.

[0082] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A cover body rubber compound, characterized in that: Including brominated butyl rubber, natural rubber, zinc oxide, magnesium oxide, accelerator, stearic acid, antioxidant, softener, reinforcing agent, Among them, the accelerator is PX.

2. The cover body rubber compound according to claim 1, characterized in that: The cover body rubber compound comprises, by weight: 60 parts of brominated butyl rubber, 40 parts of natural rubber, 8-12 parts of zinc oxide, 6.4-9.6 parts of magnesium oxide, 0.5-2.5 parts of accelerator, 0.5-2.5 parts of stearic acid, 3-6 parts of antioxidant, 3-8 parts of softener, 25-40 parts of reinforcing agent.

3. The cover rubber compound according to claim 1, characterized in that: The antioxidants include antioxidant 264 and antioxidant MB. Among them, antioxidant 264 accounts for 1-3 parts, and antioxidant MB accounts for 1-3 parts.

4. The cover rubber compound according to claim 1, characterized in that: The softener includes dioctyl sebacate and paraffin oil. Among them, paraffin oil accounts for 1-4 parts, and dioctyl sebacate accounts for 2-6 parts.

5. The cover rubber compound according to claim 1, characterized in that: The reinforcing agent is carbon black.

6. The cover rubber compound according to claim 5, characterized in that: The carbon black includes medium-super wear-resistant furnace carbon black and high wear-resistant furnace carbon black. Among them, the super wear-resistant carbon black accounts for 25-30 parts, and the high wear-resistant carbon black accounts for 1-10 parts.

7. Use of the mask body compound according to any one of claims 1 to 6 in the preparation of marine breathing masks.

8. A method for preparing the cover rubber compound according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1. Adjust the roller temperature of the mixing mill to 50-55°C for the front roller and 45-50°C for the rear roller; S2. Adjust the roller distance to 1.0-1.5 mm, add the weighed brominated butyl rubber and natural rubber into the open mill, and plasticize and press for 10-15 minutes; S3, add antioxidant 264, antioxidant MB and semi-paraffin oil into the open mill, and continue mixing for 5 to 10 minutes; S4, adjust the roller distance to 1.5-3.0 mm, add medium-super wear-resistant furnace carbon black, high wear-resistant furnace carbon black, stearic acid, and dioctyl sebacate into the mixing mill, and continue mixing for 15-20 minutes; S5. Adjust the roller distance to 3.0-4.0 mm, add medium-super wear-resistant furnace carbon black, high wear-resistant furnace carbon black, stearic acid and dioctyl sebacate into the mixing mill, and continue mixing for 15-20 minutes; S6, mix the rubber material for 10 to 15 minutes before unloading; S7, adjust the calender roller distance to 1.0-1.5mm, and the roller temperature to 30-40℃; S8. Add zinc oxide, magnesium oxide, accelerator PX and mixed rubber into the calender, mix them evenly, and cut them into sheets after mixing for 8 to 10 minutes. After cutting, isolate the sheets with pads and leave them for 4 to 168 hours to obtain the mixed rubber for the cover body.

9. The method according to claim 8, characterized in that In parts by weight, the cover body rubber mixture contains: 60 parts of brominated butyl rubber, 40 parts of natural rubber, 8-12 parts of zinc oxide, 6.4-9.6 parts of magnesium oxide, 0.5-2.5 parts of accelerator PX, 0.5-2.5 parts of stearic acid, 1.5-3 parts of antioxidant 264, 1.5-3 parts of antioxidant MB, 1.5-3 parts of paraffin oil, 2-5 parts of dioctyl sebacate, 20-50 parts of medium-super wear-resistant furnace black, and 5-8 parts of high wear-resistant furnace black.

10. A gas mask, characterized in that: The cover body compound comprises the cover body compound as described in any one of claims 1 to 6.

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