Explosion-proof and hydrolysis-resistant elastomer as well as preparation method and application thereof

Abstract

The invention discloses an anti-explosion and hydrolysis-resistant elastomer. The elastomer is prepared by mixing the following components: a polar elastomer, a styrene elastomer SEBS, mineral oil, polypropylene, a permanent antistatic agent, a long-acting antistatic agent, a filler and an antioxidant, the preparation method comprises the following steps: mixing SEBS and mineral oil in advance, fully absorbing oil, standing for half an hour, mixing other components through a high-speed mixer, adding the mixed raw materials into an extruder, extruding through double screws, cooling, and granulating to obtain plastic particles; the invention also provides the application of the anti-explosion cable on equipment in mines, chemical engineering places and high-temperature and high-humidity places with anti-explosion ATEX requirements; through the system provided by the invention, secondary injection molding coating molding with polycarbonate can be realized, and the binding force is strong; the antistatic performance can meet the ATEX explosion-proof instruction, and meanwhile, the anti-static anti-explosion paint is resistant to hydrolysis and aging in high-temperature and high-humidity environments.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly to an elastomer with explosion-proof and hydrolysis-resistant properties, a preparation method thereof, and an application thereof. Background Art

[0002] The explosion-proof ATEX directive is a series of European standards aimed at reducing the risk of fire and explosion in potentially explosive environments. These standards stipulate the manufacturing, use, and maintenance requirements of equipment used in environments where flammable substances, oxidants, and potential ignition sources exist; among them, the explosion-proof ATEX directive requires that the materials used must have antistatic properties to prevent electrostatic accumulation from triggering an explosion.

[0003] Some of the casings of gas detection devices need to use elastomer materials to meet the requirements of anti-slip and soft touch. Some elastomer materials of gas detection devices also need to be injection-molded and coated with polycarbonate (PC) for the second time to achieve a good bonding effect.

[0004] Currently, most of the elastomers injection-molded and coated with PC for the second time are basically modified from TPU or TPE. Although TPU or modified TPE has an excellent bonding effect with PC, such elastomers are prone to yellowing and will degrade in high-temperature and high-humidity environments, resulting in performance degradation. To meet the requirements of the explosion-proof ATEX directive, generally, antistatic agents are added, such as adding conductive fillers such as carbon black and graphite, or adding short-term antistatic agents; the advantage of adding carbon-based conductive fillers is low cost, and the disadvantage is that such elastomer materials can only be made black and cannot be dyed into more colors; and adding short-term antistatic agents also has the disadvantage of not being able to maintain the permanent antistatic property of the product. Summary of the Invention

[0005] The main technical problem to be solved by the present invention is to specifically develop a suitable polar elastomer, and at the same time, through the combination of preparation processes, to prepare an elastomer with explosion-proof and hydrolysis-resistant properties, which is particularly suitable for equipment in mines, chemical plants, and high-temperature and high-humidity places with explosion-proof ATEX requirements.

[0006] To solve the above technical problems, a technical solution adopted by the present invention is: to provide an elastomer with explosion-proof and hydrolysis-resistant properties, which is compounded by the following components: polar elastomer, styrenic elastomer SEBS, mineral oil, polypropylene, permanent antistatic agent, long-term antistatic agent, filler, and antioxidant.

[0007] Through the above technical solution, the difficulty in the formulation design of the present invention lies in that it is necessary to first select a suitable polar TPE, test the proportion that can have a good bonding force with PC in the system, and then adjust the hardness through SEBS and mineral oil, and test the antistatic agent content that can meet the explosion-proof ATEX directive.

[0008] Preferably, the weight ratios of the above components are as follows:

[0009]

[0010] Preferably, the polar elastomer is selected as styrene-butadiene block copolymer SBC (Styrene-butadiene block copolymer).

[0011] Preferably, the styrenic elastomer SEBS is selected as high molecular weight SEBS, and the viscosity of the SEBS toluene solution is 2000 cps to 3000 cps under the test conditions of 25 °C and 10 wt%.

[0012] Preferably, the mineral oil is selected as the mineral oil with a kinematic viscosity between 90 mm 2 / s and 100 mm 2 / s at 40 °C.

[0013] Preferably, the polypropylene is preferably selected with a melt index between 4.0 and 50 under the test conditions of 230 °C and 2.16 Kg.

[0014] Preferably, the permanent antistatic agent is selected as a high molecular type permanent antistatic agent; the long-acting antistatic agent is preferably selected as secondary alkyl sulfonate.

[0015] Preferably, the high molecular type permanent antistatic agent is selected from any one of polyether type permanent antistatic agent, quaternary ammonium salt type permanent antistatic agent, and sulfonate type permanent antistatic agent; when the high molecular type permanent antistatic agent is a polyether type permanent antistatic agent, polyethylene oxide or polyether block amide can be selected; when the high molecular type permanent antistatic agent is a quaternary ammonium salt type permanent antistatic agent, a copolymer containing a quaternary ammonium group and acrylic acid, and a copolymer containing a quaternary ammonium group and maleimide can be selected; when the high molecular type permanent antistatic agent is a sulfonate type permanent antistatic agent, sodium polystyrene sulfonate can be selected.

[0016] Preferably, the filler is selected from one or a combination of talc and calcium carbonate, and the particle size is selected to be 5 to 20 microns; the antioxidant is preferably selected as compound antioxidant 310.

[0017] To solve the above technical problems, another technical solution adopted by the present invention is as follows: The present invention provides a method for preparing an explosion-proof and hydrolysis-resistant elastomer. The preparation steps are as follows: Styrene-based elastomer SEBS is pre-mixed with mineral oil, allowed to fully absorb the oil, and then left standing for half an hour. The polar elastomer, SEBS that has absorbed the oil, polypropylene, permanent antistatic agent, long-acting antistatic agent, filler, and antioxidant are mixed by a high-speed mixer. The mixed raw materials are added to an extruder, and the processing temperature range is between 190 - 210 °C. After twin-screw extrusion, it is cooled and pelletized to obtain elastomer plastic pellets. The preparation method of the present invention system is also applicable to processing by an internal mixer or other mixing methods.

[0018] To solve the above technical problems, the present invention simultaneously adopts a third technical solution: The present invention synchronously provides an application of an explosion-proof and hydrolysis-resistant elastomer in equipment in mines, chemical plants, and high-temperature and high-humidity places with explosion-proof ATEX requirements.

[0019] The beneficial effects of the present invention are as follows:

[0020] Based on the drawbacks that the explosion-proof and hydrolysis-resistant properties of elastomers in the prior art cannot meet the usage requirements, by selecting appropriate raw material systems such as polar elastomers, styrene-based elastomer SEBS, mineral oil, antistatic agents, fillers, antioxidants, etc., using a twin-screw extruder for mixing and pelletizing, and then using an injection molding machine for sample preparation, testing hardness, mechanical properties, electrical properties, and hygrothermal aging properties, an explosion-proof and hydrolysis-resistant elastomer is prepared. The present invention achieves a better adhesion force with PC by adding different proportions of polar elastomers to the system; at the same time, by adding different proportions of antistatic agents to the system, the requirements of the ATEX directive for explosion protection are met, that is, the surface resistance is < 1.0E+09 ohm in a 50% humidity environment; through the formula system and preparation method system of the present invention, on the one hand, it can be injection-molded and coated with polycarbonate for the second time, with a strong bonding force; on the other hand, the antistatic performance can meet the ATEX explosion-proof directive; at the same time, it is hydrolysis-resistant and aging-resistant in high-temperature and high-humidity environments, especially suitable for equipment in mines, chemical plants, and high-temperature and high-humidity places with explosion-proof ATEX requirements, filling the technical gap in this aspect of elastomers, and having very good technical promotion value and market promotion value. Specific Embodiments

[0021] The following elaborates on the preferred embodiments of the present invention in detail, so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making the protection scope of the present invention more clearly defined.

[0022] Example 1:

[0023] The raw materials selected in this example are as follows: 35 parts of styrene-butadiene block copolymer SBC Styroflex2G66 (purchased from INEOS Styrolution), 22 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 22 parts of mineral oil, 10 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 1 part of long-acting antistatic agent secondary alkyl sulfonate, 10 parts of filler calcium carbonate, and 0.2 part of antioxidant 310, and they are pelletized by a twin-screw extruder.

[0024] Example 2:

[0025] The raw materials selected in this example are as follows: 35 parts of styrene-butadiene block copolymer SBC Styroflex2G66 (purchased from INEOS Styrolution), 19 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 19 parts of mineral oil, 5 parts of polypropylene, 10 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 2 parts of long-acting antistatic agent secondary alkyl sulfonate, 10 parts of filler calcium carbonate, and 0.2 part of antioxidant 310, and they are pelletized by a twin-screw extruder.

[0026] Example 3:

[0027] The raw materials selected in this example are as follows: 35 parts of styrene-butadiene block copolymer SBC Styroflex2G66 (purchased from INEOS Styrolution), 17.5 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 17.5 parts of mineral oil, 10 parts of polypropylene, 10 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 10 parts of filler calcium carbonate, and 0.2 part of antioxidant 310, and they are pelletized by a twin-screw extruder.

[0028] Example 4:

[0029] The raw materials selected in this example are as follows: 35 parts of styrene-butadiene block copolymer SBC Styroflex2G66 (purchased from INEOS Styrolution), 19.5 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 19.5 parts of mineral oil, 15 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 1 part of long-acting antistatic agent secondary alkyl sulfonate, 10 parts of filler calcium carbonate, and 0.2 part of antioxidant 310, and they are pelletized by a twin-screw extruder.

[0030] Example 5:

[0031] The raw materials selected in this example are as follows: 35 parts of styrene-butadiene block copolymer SBC Styroflex2G66 (purchased from INEOS Styrolution), 17 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 17 parts of mineral oil, 20 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 1 part of long-acting antistatic agent secondary alkyl sulfonate, 10 parts of filler calcium carbonate, and 0.2 part of antioxidant 310. They are extruded and granulated by a twin-screw extruder.

[0032] Example 6:

[0033] The raw materials selected in this example are as follows: 45 parts of styrene-butadiene block copolymer SBC Styroflex2G66 (purchased from INEOS Styrolution), 17 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 17 parts of mineral oil, 10 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 1 part of long-acting antistatic agent secondary alkyl sulfonate, 10 parts of filler calcium carbonate, and 0.2 part of antioxidant 310. They are extruded and granulated by a twin-screw extruder.

[0034] Example 7:

[0035] The raw materials selected in this example are as follows: 55 parts of styrene-butadiene block copolymer SBC Styroflex2G66 (purchased from INEOS Styrolution), 12 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 12 parts of mineral oil, 10 parts of permanent antistatic agent polyether block amide PEBAX MH2030 (purchased from Arkema, France), 1 part of long-acting antistatic agent secondary alkyl sulfonate, 10 parts of filler calcium carbonate, and 0.2 part of antioxidant 310. They are extruded and granulated by a twin-screw extruder.

[0036] The above seven groups of examples are prepared according to the following method:

[0037] Pre-mix SEBS YH-503T with mineral oil, let it fully absorb the oil and then stand for half an hour. Mix the styrene-butadiene block copolymer SBC Styroflex 2G66, the SEBS that has absorbed the oil, polypropylene, the permanent antistatic agent polyether block amide, the long-acting antistatic agent secondary alkyl sulfonate, the filler, and the antioxidant in a high-speed mixer. Add the well-mixed raw materials into the extruder, and the processing temperature range is 190 - 210°C. After twin-screw extrusion, cool and pelletize to obtain plastic pellets. The products of the present invention are also suitable for processing by an internal mixer or other mixing methods.

[0038] In addition, to more clearly demonstrate the effectiveness of the technical solution of the present invention, four sets of comparative examples are provided synchronously as follows:

[0039] Comparative Example 1

[0040] 30 parts of styrene-butadiene block copolymer SBC Styroflex 2G66 (purchased from INEOS Styrolution), 25 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 25 parts of mineral oil, 10 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 10 parts of filler calcium carbonate, 0.2 part of antioxidant 310, and granulated by a twin-screw extruder.

[0041] Comparative Example 2

[0042] 35 parts of styrene-butadiene block copolymer SBC Styroflex 2G66 (purchased from INEOS Styrolution), 22.5 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 22.5 parts of mineral oil, 7 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 13 parts of filler calcium carbonate, 0.2 part of antioxidant 310, and granulated by a twin-screw extruder.

[0043] Comparative Example 3

[0044] 35 parts of styrene-butadiene block copolymer SBC Styroflex 2G66 (purchased from INEOS Styrolution), 26.5 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 26.5 parts of mineral oil, 2 parts of long-acting antistatic agent secondary alkyl sulfonate, 10 parts of filler calcium carbonate, 0.2 part of antioxidant 310, and granulated by a twin-screw extruder.

[0045] Comparative Example 4

[0046] 35 parts of 85A polyester-based TPU Wanthane WHT-1185EC (purchased from Wanhua Chemical Group), 22.5 parts of SEBS YH-503T (purchased from Baling Petrochemical Company), 22.5 parts of mineral oil, 10 parts of permanent antistatic agent polyether block amide PEBAX MH 2030 (purchased from Arkema, France), 10 parts of filler calcium carbonate, 0.2 part of antioxidant 310, and granulated by a twin-screw extruder.

[0047] The above Examples 1, 2, 3, 4, 5, 6 and 7 are denoted as TPE1, TPE2, TPE3, TPE4, TPE5, TPE6 and TPE7. The TPE particles are injection molded into sample pieces using an injection molding machine for relevant performance test comparisons. The test data includes the following three aspects:

[0048] 1. Test the mechanical properties of the TPE in the test examples and comparative cases;

[0049] 2. Test the ATEX surface resistance performance of the TPE in the test examples and comparative cases, where the standard is: IEC 60079-0, and the surface resistance is less than 1.0E+09 ohm under the condition of 50% relative humidity;

[0050] 3. Test the resistance to damp heat aging performance of the TPE in the test examples and comparative cases, that is, put the sample pieces of the TPE in the test examples and comparative cases into a damp heat aging box at 85°C and 85% relative humidity, and check the surface state of the sample pieces after 1000 hours.

[0051] The above performance test results are shown as follows, where Table 1 is the test results corresponding to the seven groups of examples; Table 2 is the test results corresponding to the four groups of comparative examples:

[0052] Table 1. Performance test results of the sample pieces of the seven groups of examples

[0053]

[0054] Table 2. Performance test results of the sample pieces of the four groups of comparative examples

[0055]

[0056] It can be seen from all the test data that:

[0057] 1. Combining the performance test data of the above TPE1, TPE2, and TPE3, it can be known that the addition of polypropylene can increase the hardness and raise the tensile strength;

[0058] 2. Combining the performance test data of TPE1, TPE6, and TPE7, it can be known that as the content of the polar elastomer SBC increases, the bonding strength with PC also gradually increases;

[0059] 3. Combining the performance test data of the above TPE1, TPE2, and TPE3, it can be known that the addition of the long-acting antistatic agent can further reduce the surface resistance;

[0060] 4. Combining the performance test data of the above TPE1, TPE4, and TPE5, it can be known that as the content of the permanent antistatic agent increases, the surface resistance gradually decreases, and all can meet the requirements of explosion-proof ATEX;

[0061] 5. From the performance test data of Comparative Example 2 and Comparative Example 3 above, it can be seen that when the content of the permanent antistatic agent is 7 parts, or when only 2 parts of the long-acting antistatic agent is added, the surface resistance value fails to meet the requirements of the ATEX explosion-proof grade;

[0062] 6. From the performance test data of TPE1 and Comparative Example 1 above, it can be seen that when the content of the polar elastomer is only 30 parts, the bonding strength between the elastomer and PC is very low and there is no good bonding effect;

[0063] 7. From the performance test data of TPE1 and Comparative Example 4 above, it can be seen that for elastomers made of the same number of parts of the polar elastomer SBC and polyester-based TPU, the bonding strength of Comparative Example 4 is better;

[0064] 8. From the performance test data of TPE1-7 and Comparative Examples 1-4 above, it can be seen that the elastomer system based on polar SBC has a higher tolerance to high temperature and high humidity and is more hydrolysis-resistant; while the surface of Comparative Example 4 cracked, indicating that the elastomer based on polyester-based TPU is not hydrolysis-resistant.

[0065] Therefore, through the formula system and preparation method system of the present invention, an elastomer material that is explosion-proof and hydrolysis-resistant can be developed, and it can have good adhesiveness with PC, especially suitable for environments with high heat and high humidity and requiring compliance with the ATEX directive, which preferably solves the technical problems involved in the background art.

[0066] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structure or equivalent process transformation made using the content of the specification of the present invention, or directly or indirectly applied in other related technical fields, shall be similarly included in the patent protection scope of the present invention.

Claims

1. An explosion-proof and hydrolysis-resistant elastomer, characterized in that: The elastomer is prepared by mixing the following components: polar elastomer, styrene elastomer SEBS, mineral oil, polypropylene, permanent antistatic agent, long-term antistatic agent, filler and antioxidant.

2. The explosion-proof and hydrolysis-resistant elastomer according to claim 1, characterized in that: The weight ratios of the above components are as follows:

3. The explosion-proof and hydrolysis-resistant elastomer according to claim 1, characterized in that: The polar elastomer is preferably a styrene-butadiene block copolymer SBC.

4. The explosion-proof and hydrolysis-resistant elastomer according to claim 1, characterized in that: The styrene elastomer SEBS is preferably high molecular weight SEBS, and the viscosity of the toluene solution of SEBS is 2000 cps to 3000 cps under the test conditions of 25° C. and 10 wt %.

5. The explosion-proof and hydrolysis-resistant elastomer according to claim 1, characterized in that: The mineral oil preferably has a kinematic viscosity of between 90 mm at 40°C. 2 / s to 100mm 2 / s of mineral oil.

6. The explosion-proof and hydrolysis-resistant elastomer according to claim 1, characterized in that: The polypropylene preferably has a melt index of 4.0 to 50 under the test conditions of 230° C. and 2.16 kg.

7. The explosion-proof and hydrolysis-resistant elastomer according to claim 1, characterized in that: The permanent antistatic agent is a polymer permanent antistatic agent; the long-acting antistatic agent is preferably sodium secondary alkyl sulfonate.

8. The explosion-proof and hydrolysis-resistant elastomer according to claim 7, characterized in that: The polymer type permanent antistatic agent is preferably any one of a polyether type permanent antistatic agent, a quaternary ammonium salt type permanent antistatic agent, and a sulfonate type permanent antistatic agent.

9. The explosion-proof and hydrolysis-resistant elastomer according to claim 1, characterized in that: The filler is selected from talcum powder, calcium carbonate or a combination thereof, and the particle size is selected to be 5 to 20 microns; the antioxidant is preferably a compound antioxidant 310.

10. A method for preparing an explosion-proof and hydrolysis-resistant elastomer according to any one of claims 1 to 9, characterized in that: The steps include: The styrene elastomer SEBS is mixed with mineral oil in advance, and after fully absorbing the oil, it is allowed to stand for half an hour. The polar elastomer, the SEBS that has absorbed the oil, polypropylene, permanent antistatic agent, long-acting antistatic agent, filler and antioxidant are mixed by a high-speed mixer. The mixed raw materials are added to the extruder. The processing temperature range is between 190-210°C. After twin-screw extrusion, it is cooled and pelletized to obtain elastomer plastic particles.

11. Use of the explosion-proof and hydrolysis-resistant elastomer according to any one of claims 1 to 9 in equipment in mines, chemical sites, and high-temperature and high-humidity sites with explosion-proof ATEX requirements.

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