CN112321952A - Ethylene propylene diene monomer composite rubber material and preparation method thereof - Google Patents
Ethylene propylene diene monomer composite rubber material and preparation method thereof Download PDFInfo
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- CN112321952A CN112321952A CN202011210689.2A CN202011210689A CN112321952A CN 112321952 A CN112321952 A CN 112321952A CN 202011210689 A CN202011210689 A CN 202011210689A CN 112321952 A CN112321952 A CN 112321952A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
Abstract
The invention relates to an ethylene propylene diene monomer composite rubber material and a preparation method thereof, wherein the ethylene propylene diene monomer composite rubber material is mainly prepared from the following raw materials in parts by weight: 100 parts of ethylene propylene diene monomer; 30-50 parts of carbon black; 5-10 parts of modified filler; 2-3 parts of an anti-aging agent; 2.5-3 parts of an accelerant; 1.5-3 parts of a vulcanizing agent; 5-10 parts of a softener; 4-7 parts of an active agent; 1-2 parts of a processing aid; the modified filler is a base material modified by alkyl quaternary ammonium salt and a coupling agent, and the base material is one or more of montmorillonite, attapulgite and vermiculite. The ethylene propylene diene monomer composite rubber material provided by the invention can meet the requirements of high mechanical strength and low compression permanent deformation at the same time, and is simple in preparation process, low in material cost and convenient for large-scale industrial popularization.
Description
Technical Field
The invention relates to the technical field of rubber sealing materials, and particularly relates to an ethylene propylene diene monomer composite rubber material and a preparation method thereof.
Background
Ethylene Propylene Diene Monomer (EPDM) has excellent high temperature resistance, humidity and cold resistance, thermal oxidation and aging resistance, chemical medium resistance and electrical insulation, has the advantages of minimum density, large specific heat, low ablation rate, large filling property and good comprehensive performance compared with other general rubbers, and is widely applied to the fields of automobiles, aerospace, building waterproofing, outdoor facilities, communication electric power, machinery and electrical appliances, bridge structural parts, military industry and the like. The rubber for non-tires of automobiles is mainly used for manufacturing door and window sealing rubber strips, radiator rubber tubes, rubber pads, heat-resistant and oil-resistant sealing elements, protective sleeves, suspension pieces and the like, and gradually replaces other rubber types.
Ethylene propylene diene monomer is a non-self-reinforcing rubber, the strength provided by the raw rubber is limited, the tensile strength of the unfilled vulcanized rubber is low, the unfilled vulcanized rubber has no use value, and good mechanical properties need to be obtained by filling a reinforcing agent. Since some seals are subjected to a large pressure in the use environment, it is required that such rubber materials have a sufficient strength to withstand the external pressure, otherwise the rubber sealing materials are easily damaged by the pressure, resulting in the failure of the seal.
For a long time, rubber products have been filled with a large amount of a reinforcing filler such as carbon black or silica to obtain high strength, and also have disadvantages such as a decrease in elongation and a large compression set. The larger the compression set is, the poorer the sealing performance and the damping performance of the material are, and the compression set value is an important index for measuring the sealing performance and the damping performance of the rubber material and the service life of the rubber material.
Chinese patent CN103865181A discloses a rubber cup material and a preparation method thereof, wherein high wear-resistant carbon black N-330 and fast extrusion carbon black N-550 are selected as fillers, although the tensile strength of the system can reach 20MPa, the compression permanent deformation is more than 15 percent, and the elongation is low. Chinese patent CN201510738057.6 discloses a rubber material and a preparation method thereof, wherein hydrophobic fumed silica is selected as a reinforcing filler, and when 20-40 parts of hydrophobic silica is filled, the tensile strength of the system is more than or equal to 16MPa, and the compression permanent deformation is less than or equal to 15%. However, the patent needs secondary vulcanization, and the hydrophobic fumed silica is high in price, depends on import in China, is easy to generate dust and is not good for the health of operators.
Disclosure of Invention
The invention aims to: the ethylene propylene diene monomer composite rubber material can meet the requirements of high mechanical strength and low compression set at the same time, and has the advantages of simple preparation process, low material cost and convenience for large-scale industrial popularization.
In order to achieve the purpose, the invention adopts the technical scheme that:
the ethylene propylene diene composite rubber material is characterized by being mainly prepared from the following raw materials in parts by weight:
100 parts of ethylene propylene diene monomer; 30-50 parts of carbon black; 5-10 parts of modified filler; 2-3 parts of an anti-aging agent; 2.5-3 parts of an accelerant; 1.5-3 parts of a vulcanizing agent; 5-10 parts of a softener; 4-7 parts of an active agent; 1-2 parts of a processing aid;
the modified filler is a base material modified by alkyl quaternary ammonium salt and a coupling agent, and the base material is one or more of montmorillonite, attapulgite and vermiculite.
The ethylene propylene diene monomer composite rubber material provided by the invention takes ethylene propylene diene monomer as a main material, carbon black and modified filler as reinforcing filler, anti-aging agent, accelerator, vulcanizing agent, softener, activator and processing aid as auxiliary additives, the proportion of the added parts of the raw materials is adjusted in a targeted manner, and under the mutual synergistic action of the raw materials, the crosslinking density of a rubber network is improved, and the structural network is perfected and optimized, so that the final composite rubber material can achieve the advantages of high mechanical strength and low permanent deformation. The modified filler provided by the invention is a base material modified by alkyl quaternary ammonium salt and a coupling agent, the base material is a layered material which can obviously restrict molecular motion, such as montmorillonite, attapulgite, vermiculite and the like, the base material modified by the intercalation of the alkyl quaternary ammonium salt can widen the interlayer spacing of the layered material, so that molecular chains can conveniently enter, and after the modification of the coupling agent, the layered base material has good compatibility with a rubber material, and the rubber molecular chains are more easily inserted into the layered material under the shearing action and are not easy to fall off; after double bonds are grafted on the surface of the layered modified filler, the layered modified filler can react with the double bonds on rubber molecular chains under the action of an accelerant, so that the macromolecular chains are not easy to break and re-crosslink under the action of stress, the modified filler can form the physical constraint effect of molecular intercalation with rubber and can also be chemically bonded, the internal structure network of the rubber is optimized, the rubber network is effectively limited to generate large permanent deformation under high compression, a lower hysteresis effect can be generated, the strength of the rubber can be improved, and the compression permanent deformation can be reduced.
Further, the base material is montmorillonite. Researches find that the ethylene propylene diene monomer composite rubber material prepared by using the montmorillonite as the modified filler has lower water vapor transmission rate, improves the water vapor barrier capability of the rubber and has important significance for mechanical sealing and metal part anticorrosion protection application.
Further, the surface chemical group of the modified filler is a carbon-carbon double bond or a mercapto group.
Further, the weight ratio of the modified filler to the carbon black is 0.16-0.33: 1. According to the invention, carbon black and the modified filler are used as reinforcing fillers, and a great deal of experimental research of the inventor finds that the weight ratio of the modified filler to the carbon black directly influences the mechanical strength and the compression set of the final composite rubber material product. Preferably, the weight ratio of the modified filler to the carbon black is 0.2-0.3: 1. At this weight ratio, the compounded rubber material has higher mechanical strength and lower compression set.
Further, the modified filler is prepared by the following method:
putting the alkyl quaternary ammonium salt and the base material into absolute ethyl alcohol, and carrying out ultrasonic treatment at 55-70 ℃ for 0.5-1.0 h;
adding a coupling agent into the solution obtained in the step (1), performing ultrasonic treatment for 1.5-2.5 hours, standing for more than 12 hours, and drying to obtain a modified filler;
wherein, the weight of the alkyl quaternary ammonium salt accounts for more than 8 percent of the weight of the base material, and the weight of the coupling agent accounts for more than 8 percent of the weight of the base material.
The modified filler modification method provided by the invention comprises the steps of firstly modifying the base material by using alkyl quaternary ammonium salt, widening the interlayer spacing of the layered base material, facilitating the entry of molecular chains, modifying by using a coupling agent to obtain the final modified material, and controlling the coverage rate of the base material surface modifier by controlling the addition amounts of the alkyl quaternary ammonium salt and the coupling agent, thereby further adjusting the action effect of the modified filler. The method has the advantages of simple preparation method, low raw material cost and convenient popularization and application.
Further, in the step (1), the frequency of the ultrasound is 25KHz to 30 KHz.
Further, the weight of the alkyl quaternary ammonium salt accounts for 8-12% of the weight of the base material. Further, the weight of the coupling agent accounts for 8-12% of the weight of the base material. Through a large amount of experimental researches of the inventor, the addition amount of the alkyl quaternary ammonium salt and the coupling agent directly influences the functional effect of the modified filler, and researches show that the addition amount of the modifying agent reaches more than 8%, and the modified filler has an obvious functional effect, preferably, the addition amount of the modifying agent is more appropriate in the range of 8% -12%, and the addition amount exceeding 12% can cause waste of raw materials on one hand, and on the other hand, more modifying agents are added, so that the functional effect of the modified filler is not obviously improved.
Further, the alkyl quaternary ammonium salt is one or more of octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride and dioctadecyl quaternary ammonium salt.
Further, the coupling agent is one or more of gamma-methacryloxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (b-methoxyethoxy) silane.
Further, the carbon black is one or two of carbon black N330 and carbon black N220.
Further, the antioxidant comprises an amine antioxidant and a peroxide decomposition agent type antioxidant. Preferably, the anti-aging agent is one or two of anti-aging agent AW and anti-aging agent 445.
Further, the processing aid is stearic acid. Stearic acid is an aid that provides both activity and plasticizing performance.
Further, the vulcanizing agent is a mixture of sulfur and peroxide in a mass ratio of 0.8: 1-1.5: 0.5. The peroxide is one or two of DCP (dicumyl peroxide) and BIBP (di- (tert-butyl peroxy isopropyl) benzene).
Further, the activator is one or two of zinc oxide and magnesium oxide. Preferably, the activator is zinc oxide.
Further, the accelerator is a mixture of a sulfenamide accelerator and a thiuram accelerator. Further, the weight ratio of the sulfenamide accelerator to the thiuram accelerator is 2: 0.5-2.5: 0.5.
Further, the sulfenamide-based accelerator is one or more of N-t-butyl-2-benzothiazolesulfenamide (NS), N-cyclohexyl-2-benzothiazolesulfenamide (CZ), N dicyclohexyl-2-benzothiazolesulfenamide (DZ), N-oxydiethylene-2-benzothiazolesulfenamide (NOBS) and N-oxydiethylene thiocarbamoyl-N' -oxydiethylene sulfenamide (OTOS).
Further, the thiuram accelerators are one or more of tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), bis (1, 5-pentamethylene) thiuram tetrasulfide (DPTT).
Preferably, the sulfenamide-based accelerator is NOBS (N- (oxydiethylene) -2-benzothiazolesulfenamide) and the thiuram-based accelerator is TMTM (tetramethylthiuram monosulfide).
The invention also aims to provide a preparation method of the ethylene propylene diene monomer composite rubber material.
A preparation method of an ethylene propylene diene monomer composite rubber material comprises the following steps:
step 1, putting ethylene propylene diene monomer rubber into an internal mixer according to the raw material ratio for plastication for 3-5 min, adding modified filler at the temperature of 100-110 ℃ and continuously plasticating for more than 8min to obtain a first rubber material;
step 2, adding carbon black, a processing aid, an anti-aging agent and a softening agent into the first rubber material obtained in the step 1 in sequence, and plastifying at 100-110 ℃ for 3-5 min to obtain a second rubber material;
step 3, adding an active agent into the second rubber compound obtained in the step 2, and plasticating for more than 8min at the temperature of 115-125 ℃ to obtain a third rubber compound;
step 4, taking the third rubber compound obtained in the step 3 out of the open mill, cooling to 50-60 ℃, sequentially adding an accelerator and a vulcanizing agent, mixing and plasticating to obtain a fourth rubber compound;
and 5, standing the fourth rubber material obtained in the step 4 for more than 12 hours, and vulcanizing at the temperature of 130-150 ℃ and the pressure of 10-15 MPa for 60-75 minutes to obtain the ethylene propylene diene monomer composite rubber material.
The preparation method of the ethylene propylene diene monomer composite rubber material provided by the invention does not need multiple vulcanization, has simple process and low raw material cost, and is beneficial to large-scale industrialized popularization.
Further, in the step 1, in the plastication process, the rotating speed of the internal mixer is 40-50 r/min. The reasonable rotating speed of the internal mixer is beneficial to more uniform and effective plastication in the plastication process.
Further, in the step 1, the modified filler is added at the temperature of 100-120 ℃ for continuous plastication for 8-12 min.
Further, in the step 2, in the plastication process, the rotating speed of the internal mixer is 40-50 r/min.
Further, in the step 3, in the plastication process, the rotating speed of the internal mixer is 40-50 r/min.
Further, in the step 3, an active agent is added into the second rubber compound obtained in the step 2, and plastication is carried out for 8min to 12min at the temperature of 115 ℃ to 125 ℃.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the ethylene propylene diene monomer composite rubber material provided by the invention takes ethylene propylene diene monomer as a main material, carbon black and modified filler as reinforcing filler, anti-aging agent, accelerator, vulcanizing agent, softener, activator and processing aid as auxiliary additives, the proportion of the added parts of the raw materials is adjusted in a targeted manner, and under the mutual synergistic action of the raw materials, the crosslinking density of a rubber network is improved, and the structural network is perfected and optimized, so that the final composite rubber material can simultaneously achieve good material properties of 20MPa of tensile strength and 9% of compression permanent deformation.
2. The modified filler provided by the invention is a base material modified by alkyl quaternary ammonium salt and a coupling agent, the base material is a layered material which can obviously restrict molecular motion, such as montmorillonite, attapulgite, vermiculite and the like, the base material modified by the intercalation of the alkyl quaternary ammonium salt can widen the interlayer spacing of the layered material, so that molecular chains can conveniently enter, and after the modification of the coupling agent, the layered base material has good compatibility with a rubber material, and the rubber molecular chains are more easily inserted into a lamellar material under the shearing action and are not easy to fall off; after double bonds are grafted on the surface of the layered modified filler, the layered modified filler can react with the double bonds on rubber molecular chains under the action of an accelerant, so that the macromolecular chains are not easy to break and re-crosslink under the action of stress, the modified filler can form the physical constraint effect of molecular intercalation with rubber and can also be chemically bonded, the internal structure network of the rubber is optimized, the rubber network is effectively limited to generate large permanent deformation under high compression, a lower hysteresis effect can be generated, the strength of the rubber can be improved, and the compression permanent deformation can be reduced.
3. The modified filler modification method provided by the invention comprises the steps of firstly modifying the base material by using alkyl quaternary ammonium salt, widening the interlayer spacing of the layered base material, facilitating the entry of molecular chains, modifying by using a coupling agent to obtain the final modified material, and controlling the coverage rate of the base material surface modifier by controlling the addition amounts of the alkyl quaternary ammonium salt and the coupling agent, thereby further adjusting the action effect of the modified filler. The method has the advantages of simple preparation method, low raw material cost and convenient popularization and application.
4. The preparation method of the ethylene propylene diene monomer composite rubber material provided by the invention does not need multiple vulcanization, has simple process and low raw material cost, and is beneficial to large-scale industrialized popularization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The reagents used in the following examples and comparative examples of the invention were obtained from commercial products, some of which were as follows: anti-aging agent AW (Dongguan Owen New Material Co., Ltd.), anti-aging agent 445 (Dongguan Owen New Material Co., Ltd.), NOBS (Dongguan Owen New Material Co., Ltd.), DCP (Dongguan Owen New Material Co., Ltd.), A172 (Dongguan Owen New Material Co., Ltd.)
Example 1
Preparation of modified montmorillonite
Putting 10 parts of octadecyl trimethyl ammonium chloride and 100 parts of montmorillonite into absolute ethyl alcohol, and performing ultrasonic treatment at 60 ℃ for 0.5 h; wherein, the frequency in the ultrasonic process is 25 KHz; adding 8 parts of vinyl trimethoxy silane into the solution obtained in the step (1), carrying out ultrasonic treatment for 2 hours, standing for 24 hours, and drying to obtain the modified montmorillonite.
Preparation of ethylene propylene diene composite rubber material
And (3) plasticating 100 parts of ethylene propylene diene monomer in an internal mixer at the rotating speed of 40r/min for 3 minutes, raising the temperature of the internal mixer to 110 ℃, adding 8 parts of modified montmorillonite, and continuously carrying out internal mixing for 10 minutes to carry out molecular chain intercalation. Then, 40 parts of carbon black, 1.5 parts of stearic acid, 1.25 parts of an anti-aging agent AW, 1.25 parts of an anti-aging agent 445 and 8 parts of paraffin oil are sequentially added, the mixture is kept at 110 ℃ for banburying for 3 minutes at the rotating speed of 40-50 r/min, then 6 parts of zinc oxide is added, the temperature of an internal mixer is raised to 120 ℃ for banburying for 10 minutes at the rotating speed of 40-50 r/min, finally, the mixture is taken out of a piece on an open mill and cooled to 60 ℃, 2 parts of NOBS, 0.5 part of TMTM, 0.8 part of sulfur and 1 part of DCP are sequentially added, and the mixture is uniformly mixed. Standing for 24h, carrying out flat plate mould pressing vulcanization to obtain vulcanized rubber, wherein the vulcanization temperature is 150 ℃, the vulcanization time is 60 minutes, and the vulcanization pressure is 10MPa, so that the ethylene propylene diene monomer composite rubber material is obtained.
Example 2
Preparation of modified Attapulgite
Putting 12 parts of dioctadecyl quaternary ammonium salt and 100 parts of attapulgite into absolute ethyl alcohol, and performing ultrasonic treatment for 1 hour at 55 ℃; wherein, the frequency in the ultrasonic process is 30 KHz; and (2) adding 10 parts of mercaptopropyl trimethoxy silane into the solution obtained in the step (1), performing ultrasonic treatment for 1.5h, standing for 20h, and drying to obtain the modified attapulgite.
Preparation of ethylene propylene diene composite rubber material
And (3) plasticating 100 parts of ethylene propylene diene monomer in an internal mixer at the rotating speed of 45r/min for 4 minutes, heating the internal mixer to 100 ℃, adding 9 parts of modified attapulgite, and continuously carrying out internal mixing for 8 minutes to carry out molecular chain intercalation. Then, 50 parts of carbon black, 1 part of stearic acid, 1.5 parts of an anti-aging agent AW, 1.5 parts of an anti-aging agent 445 and 5 parts of paraffin oil are sequentially added, the mixture is kept at 105 ℃ for banburying for 4 minutes at the rotating speed of 45r/min, then 4 parts of zinc oxide are added, the temperature of a banbury mixer is raised to 115 ℃ for banburying for 10 minutes at the rotating speed of 45r/min, finally, the mixture is taken out of a piece on an open mill and cooled to 50 ℃, 2.5 parts of NOBS, 0.5 part of TMTM, 1.0 part of sulfur and 2.0 parts of DCP are sequentially added, and the mixture is uniformly mixed. Standing for 12h, carrying out flat plate mould pressing vulcanization to obtain vulcanized rubber, wherein the vulcanization temperature is 130 ℃, the vulcanization time is 65 minutes, and the vulcanization pressure is 15MPa, so that the ethylene propylene diene monomer composite rubber material is obtained.
Example 3
Preparation of modified vermiculite
Putting 10 parts of octadecyl dimethyl benzyl ammonium chloride and 100 parts of vermiculite into absolute ethyl alcohol, and performing ultrasonic treatment at 60 ℃ for 1 hour; wherein, the frequency in the ultrasonic process is 25 KHz; and (2) adding 12 parts of vinyltriethoxysilane into the solution obtained in the step (1), performing ultrasonic treatment for 1.5 hours, standing for 20 hours, and drying to obtain the modified vermiculite.
Preparation of ethylene propylene diene composite rubber material
And (3) placing 100 parts of ethylene propylene diene monomer rubber into an internal mixer for plasticating for 5 minutes at the rotating speed of 50r/min, raising the temperature of the internal mixer to 105 ℃, adding 5 parts of modified vermiculite, and continuing to carry out internal mixing for 12 minutes to carry out molecular chain intercalation. Then, 30 parts of carbon black, 1 part of stearic acid, 1 part of antioxidant AW, 1 part of antioxidant 445 and 8 parts of paraffin oil are sequentially added, the mixture is kept at 110 ℃ for banburying for 5 minutes at the rotating speed of 45r/min, then 4 parts of zinc oxide are added, the temperature of a banbury mixer is raised to 125 ℃ for banburying for 12 minutes at the rotating speed of 40-50 r/min, finally, the mixture is taken out of a piece on an open mill and cooled to 55 ℃, 2 parts of NOBS, 0.5 part of TMTM, 0.5 part of sulfur and 1 part of DCP are sequentially added, and the mixture is uniformly mixed. Standing for 18h, carrying out flat plate mould pressing vulcanization to obtain vulcanized rubber, wherein the vulcanization temperature is 140 ℃, the vulcanization time is 75 minutes, and the vulcanization pressure is 14MPa, so that the ethylene propylene diene monomer composite rubber material is obtained.
Comparative examples 1 to 2 and examples 4 to 7
Comparative examples 1-2 and examples 4-7 compared with example 1, the weight ratio of the modified montmorillonite and the carbon black was changed, the total weight of the modified montmorillonite and the carbon black was the same as that of example 1, and the preparation method of the modified montmorillonite, the composition of other raw materials, the weight parts of other raw materials and the preparation method of the composite rubber material were the same as that of example 1. The fractions and weight ratios of the modified montmorillonite, carbon black of comparative examples 1-2 and examples 4-7 are shown in Table 1.
TABLE 1 raw material ratio
Comparative example 3 (modified Filler not used)
Comparative example 3 compared with example 1, no modified filler is used, the use part of the carbon black filler in the comparative example 3 is the sum of the parts of the carbon black and the modified montmorillonite in the example 1, and the other raw material compositions, the addition amounts and the preparation process are the same as those in the example 1.
Preparation of ethylene propylene diene composite rubber material
Putting 100 parts of ethylene propylene diene monomer rubber into an internal mixer for plasticating for 3 minutes at the rotating speed of 40r/min, raising the temperature of the internal mixer to 110 ℃, then sequentially adding 48 parts of carbon black, 1.5 parts of stearic acid, 1.25 parts of antioxidant AW, 1.25 parts of antioxidant 445 and 8 parts of paraffin oil, keeping the internal mixer at 110 ℃ for 3 minutes at the rotating speed of 40-50 r/min, then adding 6 parts of zinc oxide, raising the temperature of the internal mixer to 120 ℃ for 10 minutes at the rotating speed of 40-50 r/min, finally taking out a piece from an open mill, cooling to 60 ℃, sequentially adding 2 parts of NOBS, 0.5 part of TMTM, 0.8 part of sulfur and 1 part of DCP, and uniformly mixing. Standing for 24h, carrying out flat plate mould pressing vulcanization to obtain vulcanized rubber, wherein the vulcanization temperature is 150 ℃, the vulcanization time is 60 minutes, and the vulcanization pressure is 10MPa, so that the ethylene propylene diene monomer composite rubber material is obtained.
Comparative example 4 (replacement of modified Filler by inorganic Filler)
Comparative example 4 compared with example 1, modified montmorillonite was replaced with inorganic filler calcium carbonate, and the other raw materials of comparative example 4 were the same in composition, addition amount and preparation process as example 1.
Preparation of ethylene propylene diene composite rubber material
And (3) placing 100 parts of ethylene propylene diene monomer rubber into an internal mixer for plasticating for 3 minutes at the rotating speed of 40r/min, raising the temperature of the internal mixer to 110 ℃, adding 8 parts of calcium carbonate, and continuing to perform internal mixing for 10 minutes to perform molecular chain intercalation. Then, 40 parts of carbon black, 1.5 parts of stearic acid, 1.25 parts of an anti-aging agent AW, 1.25 parts of an anti-aging agent 445 and 8 parts of paraffin oil are sequentially added, the mixture is kept at 110 ℃ for banburying for 3 minutes at the rotating speed of 40-50 r/min, then 6 parts of zinc oxide is added, the temperature of an internal mixer is raised to 120 ℃ for banburying for 10 minutes at the rotating speed of 40-50 r/min, finally, the mixture is taken out of a piece on an open mill and cooled to 60 ℃, 2 parts of NOBS, 0.5 part of TMTM, 0.8 part of sulfur and 1 part of DCP are sequentially added, and the mixture is uniformly mixed. Standing for 24h, carrying out flat plate mould pressing vulcanization to obtain vulcanized rubber, wherein the vulcanization temperature is 150 ℃, the vulcanization time is 60 minutes, and the vulcanization pressure is 10MPa, so that the ethylene propylene diene monomer composite rubber material is obtained.
Comparative example 5 (phenol type antioxidant)
Comparative example 5 compared with example 1 to replace antioxidant AW and antioxidant 445 to phenolic antioxidant SP, comparative example 5 other raw material composition and addition amount, preparation process and example 1 the same.
And (3) placing 100 parts of ethylene propylene diene monomer rubber into an internal mixer for plasticating for 3 minutes at the rotating speed of 40r/min, raising the temperature of the internal mixer to 110 ℃, adding 8 parts of calcium carbonate, and continuing to perform internal mixing for 10 minutes to perform molecular chain intercalation. Then, 40 parts of carbon black, 1.5 parts of stearic acid, 2.5 parts of antioxidant SP and 8 parts of paraffin oil are sequentially added, the mixture is kept at 110 ℃ for banburying for 3 minutes at the rotating speed of 40-50 r/min, then 6 parts of zinc oxide is added, the temperature of a banbury mixer is raised to 120 ℃ for banburying for 10 minutes at the rotating speed of 40-50 r/min, finally, the mixture is taken out of a piece on an open mill and cooled to 60 ℃, 2 parts of NOBS, 0.5 part of TMTM, 0.8 part of sulfur and 1 part of DCP are sequentially added, and the mixture is uniformly mixed. Standing for 24h, carrying out flat plate mould pressing vulcanization to obtain vulcanized rubber, wherein the vulcanization temperature is 150 ℃, the vulcanization time is 60 minutes, and the vulcanization pressure is 10MPa, so that the ethylene propylene diene monomer composite rubber material is obtained.
COMPARATIVE EXAMPLE 6 (coupling agent)
Group A: preparation of modified montmorillonite
Putting 10 parts of octadecyl trimethyl ammonium chloride and 100 parts of montmorillonite into absolute ethyl alcohol, and performing ultrasonic treatment at 60 ℃ for 0.5 h; wherein, the frequency in the ultrasonic process is 25 KHz; adding 6 parts of vinyl trimethoxy silane into the solution obtained in the step (1), carrying out ultrasonic treatment for 2 hours, standing for 24 hours, and drying to obtain the modified montmorillonite.
Group B: preparation of modified montmorillonite
Putting 6 parts of octadecyl trimethyl ammonium chloride and 100 parts of montmorillonite into absolute ethyl alcohol, and performing ultrasonic treatment at 60 ℃ for 0.5 h; wherein, the frequency in the ultrasonic process is 25 KHz; adding 8 parts of vinyl trimethoxy silane into the solution obtained in the step (1), carrying out ultrasonic treatment for 2 hours, standing for 24 hours, and drying to obtain the modified montmorillonite.
In comparison with the modified montmorillonite prepared in example 1, the group A and the group B in the comparative example 6 respectively change the addition ratio of the coupling agent and the alkyl quaternary ammonium salt, and prepare the ethylene-propylene-diene composite rubber material according to the preparation method, the process parameters and the raw materials which are the same as those in example 1.
The ethylene propylene diene monomer composite rubber materials prepared in comparative examples 1 to 6 and examples 1 to 7 were subjected to the tests of the physical properties of tensile strength, tensile elongation, hardness, compression set, water vapor transmission rate according to the following test standards:
the tensile strength and elongation of the rubber material were tested using GB/T528-2009.
The hardness of the rubber material was tested using GB/T531.1-2008.
The compression set of the rubber material was tested by the method GB/T7759 and 1996A.
The water vapor transmission rate of the rubber material is tested by GB/T21529-.
The results of the physical property tests of the ethylene-propylene-diene composite rubber materials prepared in comparative examples 1 to 6 and examples 1 to 7 are shown in Table 2.
TABLE 2 physical Properties of EPDM composite rubber Material
From the physical property test results in table 2, it can be seen that the tensile strength of the ethylene-propylene-diene monomer composite rubber materials prepared in examples 1-3 is above 16MPa, and the compression permanent deformation is below 12%, the composite rubber material provided by the invention takes carbon black and modified filler as reinforcing filler, and under the mutual synergistic action of the raw materials, the cross-linking density of a rubber network is improved, and the structural network is perfected and optimized, so that the final composite rubber material can achieve the advantages of high mechanical strength and low permanent deformation, and meanwhile, the water vapor permeability is obviously lower than that of modified attapulgite and vermiculite when the modified filler is modified montmorillonite.
From the physical property test results of the products of comparative examples 1-2 and examples 4-7, it can be seen that the weight ratio of the modified filler to the carbon black directly affects the mechanical strength and the compression set of the final composite rubber material product, and when the weight ratio of the modified filler to the carbon black is 0.16-0.33: 1, the tensile strength of the prepared ethylene propylene diene monomer composite rubber material is more than 17MPa, and the compression set is less than 13%. When the weight ratio of the modified filler to the carbon black is lower than 0.16:1 and higher than 0.33:1, the mechanical strength of the composite rubber material is obviously reduced, and the compression permanent deformation is obviously increased, preferably, when the weight ratio of the modified filler to the carbon black is 0.2-0.3: 1, the composite rubber material product shows better physical properties, and can simultaneously reach the tensile strength of 20MPa and the compression permanent deformation of 9%. Comparative example 3 is the use of modified filler, only carbon black as reinforcing filler, low mechanical strength, large compression set, low water vapor permeability, and reduced product performance.
Comparative example 4 carbon black and calcium carbonate were used as reinforcing fillers, the mechanical strength was low, the compression set was large, the water permeability to moisture was low, and the product performance was reduced. The comparison example 5 uses the phenol antioxidant SP, has low mechanical strength and large compression permanent deformation, and the performance of the ethylene propylene diene monomer composite rubber material product is reduced. In the group A and the group B in the comparative example 6, compared with the modified montmorillonite prepared in the example 1, the addition ratio of the coupling agent and the alkyl quaternary ammonium salt is respectively changed, and researches show that when the addition amount of the coupling agent and the alkyl quaternary ammonium salt is 8 percent lower than that of the base material in the process of preparing the modified material, the performance effect of the modified filler is reduced, and the material performance of the composite rubber material is directly caused to be not up to the standard.
The modified filler provided by the invention is a base material modified by alkyl quaternary ammonium salt and a coupling agent, the base material is a layered material which can obviously restrict molecular motion, such as montmorillonite, attapulgite, vermiculite and the like, the base material modified by the intercalation of the alkyl quaternary ammonium salt can widen the interlayer spacing of the layered material, so that molecular chains can conveniently enter, and after the modification of the coupling agent, the layered base material has good compatibility with a rubber material, and the rubber molecular chains are more easily inserted into a lamellar material under the shearing action and are not easy to fall off; after double bonds are grafted on the surface of the layered modified filler, the layered modified filler can react with the double bonds on rubber molecular chains under the action of an accelerant, so that the macromolecular chains are not easy to break and re-crosslink under the action of stress, the modified filler can form the physical constraint effect of molecular intercalation with rubber and can also be chemically bonded, the internal structure network of the rubber is optimized, the rubber network is effectively limited to generate large permanent deformation under high compression, a lower hysteresis effect can be generated, the strength of the rubber can be improved, and the compression permanent deformation can be reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The ethylene propylene diene composite rubber material is characterized by being mainly prepared from the following raw materials in parts by weight:
100 parts of ethylene propylene diene monomer; 30-50 parts of carbon black; 5-10 parts of modified filler; 2-3 parts of an anti-aging agent; 2.5-3 parts of an accelerant; 1.5-3 parts of a vulcanizing agent; 5-10 parts of a softener; 4-7 parts of an active agent; 1-2 parts of a processing aid;
the modified filler is a base material modified by alkyl quaternary ammonium salt and a coupling agent, and the base material is one or more of montmorillonite, attapulgite and vermiculite.
2. The ethylene-propylene-diene monomer composite rubber material as claimed in claim 1, wherein the weight ratio of the modified filler to the carbon black is 0.16-0.33: 1.
3. The ethylene-propylene-diene monomer composite rubber material as claimed in claim 2, wherein the weight ratio of the modified filler to the carbon black is 0.2-0.3: 1.
4. The ethylene propylene diene composite rubber material according to claim 1, wherein the modified filler is prepared by the following method:
putting the alkyl quaternary ammonium salt and the base material into absolute ethyl alcohol, and carrying out ultrasonic treatment at 55-70 ℃ for 0.5-1.0 h;
adding a coupling agent into the solution obtained in the step (1), performing ultrasonic treatment for 1.5-2.5 hours, standing for more than 12 hours, and drying to obtain a modified filler;
wherein, the weight of the alkyl quaternary ammonium salt accounts for more than 8 percent of the weight of the base material, and the weight of the coupling agent accounts for more than 8 percent of the weight of the base material.
5. The ethylene-propylene-diene monomer composite rubber material as claimed in claim 4, wherein the weight of the alkyl quaternary ammonium salt accounts for 8-12% of the weight of the base material, and the weight of the coupling agent accounts for 8-12% of the weight of the base material.
6. The ethylene-propylene-diene composite rubber material of claim 1, wherein the alkyl quaternary ammonium salt is one or more of octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride and dioctadecyl quaternary ammonium salt;
the coupling agent is one or more of gamma-methacryloxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (b-methoxyethoxy) silane.
7. The ethylene-propylene-diene monomer composite rubber material according to claim 1, wherein the antioxidant comprises an amine antioxidant and a peroxide decomposer type antioxidant.
8. The ethylene-propylene-diene monomer composite rubber material according to claim 1, wherein the vulcanizing agent is a mixture of sulfur and peroxide in a mass ratio of 0.8:1 to 1.5: 0.5.
9. The ethylene-propylene-diene monomer composite rubber material according to claim 1, wherein the accelerator is a mixture of a sulfenamide accelerator and a thiuram accelerator; wherein the sulfenamide-based accelerator is one or more of N-tert-butyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-dicyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, and N-oxydiethylene thiocarbamoyl-N' -oxydiethylene sulfenamide; the thiuram accelerator is one or more of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide and bis (1, 5-pentamethylene) thiuram tetrasulfide.
10. A method for preparing an ethylene-propylene-diene monomer composite rubber material according to any one of claims 1 to 9, characterized by comprising the following steps:
step 1, putting ethylene propylene diene monomer rubber into an internal mixer according to the raw material ratio for plastication for 3-5 min, adding modified filler at the temperature of 100-110 ℃ and continuously plasticating for more than 8min to obtain a first rubber material;
step 2, adding carbon black, a processing aid, an anti-aging agent and a softening agent into the first rubber material obtained in the step 1 in sequence, and plastifying at 100-110 ℃ for 3-5 min to obtain a second rubber material;
step 3, adding an active agent into the second rubber compound obtained in the step 2, and plasticating for more than 8min at the temperature of 115-125 ℃ to obtain a third rubber compound;
step 4, taking the third rubber compound obtained in the step 3 out of the open mill, cooling to 50-60 ℃, sequentially adding an accelerator and a vulcanizing agent, mixing and plasticating to obtain a fourth rubber compound;
and 5, standing the fourth rubber material obtained in the step 4 for more than 12 hours, and vulcanizing at the temperature of 130-150 ℃ and the pressure of 10-15 MPa for 60-75 minutes to obtain the ethylene propylene diene monomer composite rubber material.
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