CN112920516B - Low-pressure-change EPDM sealing element capable of being rapidly peroxidized and vulcanized at high temperature and preparation method thereof - Google Patents

Low-pressure-change EPDM sealing element capable of being rapidly peroxidized and vulcanized at high temperature and preparation method thereof Download PDF

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CN112920516B
CN112920516B CN202110124781.5A CN202110124781A CN112920516B CN 112920516 B CN112920516 B CN 112920516B CN 202110124781 A CN202110124781 A CN 202110124781A CN 112920516 B CN112920516 B CN 112920516B
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agent
percent
high temperature
peroxide
peroxidized
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CN112920516A (en
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李锦杰
张德富
郑华安
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XIAMEN MAIFENG SEAL PRODUCTS CO Ltd
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XIAMEN MAIFENG SEAL PRODUCTS CO Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The invention relates to the technical field of rubber, and in particular provides a low-pressure-change EPDM sealing element capable of being rapidly peroxidized and vulcanized at a high temperature and a preparation method thereof. The invention provides a low-pressure-change EPDM sealing element capable of being rapidly peroxidized and vulcanized at high temperature, which comprises the following raw materials in percentage by weight: 35 to 45 percent of ethylene propylene diene monomer, 35 to 45 percent of filler, 5 to 10 percent of softener, 0.5 to 0.8 percent of anti-aging agent, 3.7 to 5 percent of active agent, 1 to 2 percent of heat conducting agent, 0.8 to 1.2 percent of flow aid, 0.4 to 0.6 percent of peroxide bridging agent and the balance of peroxide vulcanizing agent.

Description

Low-pressure-change EPDM sealing element capable of being rapidly peroxidized and vulcanized at high temperature and preparation method thereof
Technical Field
The invention relates to the field of rubber, and in particular provides a low-pressure-change EPDM sealing element capable of being rapidly peroxidized and vulcanized at high temperature and a preparation method thereof.
Background
Ethylene propylene rubber is a synthetic rubber which has been developed after the development of ziegler-natta stereoregular catalytic systems, and which is intermediate between general purpose rubber and specialty rubber. The ethylene propylene diene monomer has outstanding ozone resistance and weather resistance, excellent heat resistance, electrical insulation performance and good chemical stability, and the EPDM has small density and can be filled with a large amount of filler and softener, so that the ethylene propylene diene monomer can be used for preparing products with competitive advantages in performance and cost, and is widely applied to the fields of automobile parts, tires, waterproof coiled materials, wires and cables, household appliances and other rubber sundries.
At present, a sulfur vulcanization system and a peroxide vulcanization system are mainly adopted, wherein the sulfur vulcanization system has high vulcanization speed, excellent physical and mechanical properties of vulcanized rubber and most common application, but the required compounding agents are more, the sanitary performance cannot be met, the compression set is larger, and the heat resistance is poorer; the EPDM peroxidized product has the advantages of excellent heat aging resistance, excellent compression resistance, good color stability, no scorching hazard during storage of rubber materials, high rebound resilience and the like. But EPDM peroxide cure systems are typical of "fast start-up, slow speed" systems, which are disadvantageous to increase the efficiency of the cure process and are a cost disadvantage. Thus, rationalizing the vulcanization process while achieving higher physical properties is a very important issue. In view of this problem, the present invention is directed to developing a low pressure change EPDM seal material that can be rapidly peroxide cured at high temperatures.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a low-pressure-change EPDM sealing member capable of being rapidly peroxidized and vulcanized at high temperature, which comprises the following preparation raw materials in percentage by weight: 35 to 45 percent of ethylene propylene diene monomer, 35 to 45 percent of filler, 5 to 10 percent of softener, 0.5 to 0.8 percent of anti-aging agent, 3.7 to 5 percent of active agent, 1 to 2 percent of heat conducting agent, 0.8 to 1.2 percent of flow aid, 0.4 to 0.6 percent of peroxide bridging agent and the balance of peroxide vulcanizing agent.
As a preferable technical scheme of the invention, the Mooney viscosity value of the ethylene propylene diene monomer is 26-32, wherein the ethylene content is 45-56%, and the ethylidene norbornene content of the third monomer is 3.8-4.5%.
As a preferable technical scheme of the invention, the filler is selected from one or a combination of more of carbon black, silica powder, clay, kaolin and silica micropowder.
As a preferable technical scheme of the invention, the anti-aging agent is selected from one or a combination of more than one of 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, 2-mercaptobenzimidazole and 2, 4-trimethyl-1, 2-dihydroquinoline polymer.
As a preferred embodiment of the present invention, the anti-aging agent comprises 2-mercaptobenzimidazole and 4,4' -bis (α, α -dimethylbenzyl) diphenylamine; the mass ratio of the 2-mercaptobenzimidazole to the 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine is 1: (0.8-1.2).
As a preferable technical scheme of the invention, the active agent is selected from one or a combination of more of zinc oxide, zinc stearate, calcium oxide, calcium chloride and barium chloride.
As a preferred embodiment of the present invention, the active agent includes zinc oxide and zinc stearate; the mass ratio of the zinc oxide to the zinc stearate is 4: (0.2-0.4).
As a preferable technical scheme of the invention, the heat conducting agent is active magnesium oxide; the specific surface area of the active magnesium oxide is 140-150 m 2 /g。
As a preferable technical scheme of the invention, the peroxide vulcanizing agent is selected from one or a combination of more of benzoyl peroxide, 2, 5-dimethyl-2, 5-di (benzoyl peroxide) hexane, tert-butyl peroxybenzoate, 1, 4-di-tert-butyl peroxydiisopropylbenzene, diisopropylbenzene peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane.
The second aspect of the invention provides a method for preparing a low-pressure-change EPDM sealing member capable of being rapidly peroxidized and vulcanized at high temperature, which at least comprises the following steps:
(1) Adding ethylene propylene diene monomer into an internal mixer, banburying, sequentially adding a filler, a softener, an active agent, an anti-aging agent, a heat conducting agent and a flow aid, banburying, discharging after uniform mixing, and cooling to obtain master batch;
(2) Putting the masterbatch into an open mill, adding a peroxide bridging agent and a peroxide vulcanizing agent, mixing, discharging sheets, and cooling by a cooling machine to obtain a final rubber sheet;
(3) Cutting the final rubber sheet into required model products, heating a die by a vacuum plate vulcanizing machine, putting the rubber sheet into a die cavity of the die to be matched with the die for primary vulcanization, and taking out a finished product after primary vulcanization;
(4) And (3) performing secondary vulcanization on the finished product, and obtaining the finished product after secondary vulcanization.
The beneficial effects are that: the invention takes the special ethylene propylene diene monomer as the base material, and selects the special filler, the active agent, the anti-aging agent and the like during the preparation by selecting and controlling the contents, further controls the respective contents, and synergistically enhances the fluidity and the heat conductivity of the material under the action of the peroxide bridging agent, the peroxide vulcanizing agent and other components, thereby rapidly filling the die cavity and ensuring the material to realize rapid and full vulcanization under the high-temperature environment; the compression set of the material can be reduced, the production efficiency is improved, the peroxide consumption is reduced, the cost is reduced, and the method plays an important role in sustainable development of EPDM rubber materials in the water sealing industry.
Detailed Description
The contents of the present invention can be more easily understood by referring to the following detailed description of preferred embodiments of the present invention and examples included. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component also includes the plural reference unless the amount is obvious to the singular reference.
In order to solve the technical problems, the first aspect of the invention provides a low-pressure-change EPDM sealing member capable of being rapidly peroxidized and vulcanized at high temperature, which comprises the following preparation raw materials in percentage by weight: 35 to 45 percent of ethylene propylene diene monomer, 35 to 45 percent of filler, 5 to 10 percent of softener, 0.5 to 0.8 percent of anti-aging agent, 3.7 to 5 percent of active agent, 1 to 2 percent of heat conducting agent, 0.8 to 1.2 percent of flow aid, 0.4 to 0.6 percent of peroxide bridging agent and the balance of peroxide vulcanizing agent.
In a preferred embodiment, the preparation raw materials comprise at least, in weight percent: 40% of ethylene propylene diene monomer rubber, 40% of filler, 7% of softener, 0.6% of anti-aging agent, 4.3% of active agent, 1.5% of heat conducting agent, 1% of flow aid, 0.5% of peroxide bridging agent and the balance of peroxide vulcanizing agent.
<Ethylene propylene diene monomer>
The ethylene propylene diene monomer copolymer of the invention is ethylene propylene rubber, and a small amount of non-conjugated diene, and is represented by EPDM (Ethylene Propylene Diene Monomer), and because the main chain of the ethylene propylene diene monomer copolymer is composed of chemically stable saturated hydrocarbon and only contains unsaturated double bonds in side chains, the ethylene propylene diene monomer copolymer has excellent ageing resistance such as ozone resistance, heat resistance, weather resistance and the like, and can be widely applied to the fields of automobile parts, waterproof materials for buildings, wire and cable sheaths, heat-resistant rubber tubes, adhesive tapes, automobile sealing parts and the like.
In one embodiment, the ethylene propylene diene monomer has a mooney viscosity value of 26 to 32, wherein the ethylene content is 45 to 56%, and the ethylidene norbornene content of the third monomer is 3.8 to 4.5%.
In a preferred embodiment, the ethylene propylene diene monomer has a mooney viscosity number of 28, wherein the ethylene content is 48% and the ethylidene norbornene third monomer is 4.1%.
In a more preferred embodiment, the ethylene propylene diene monomer is purchased from Arrheniaceae 2450, lanxess chemical Co., ltd.
The Mooney viscosity values were measured at ML (1+4) 125. DegreeC. The invention is not limited to the measurement method, wherein M represents Mooney, L represents a large rotor, 1 represents preheating for 1 minute, and 4 represents a test for 4 minutes.
The content is mass content.
<Filler (B)>
The filler is one or a combination of more of carbon black, silica powder, clay, kaolin and silica micropowder.
In a preferred embodiment, the filler comprises carbon black and silicone powder.
In a more preferred embodiment, the mass ratio of carbon black to silicone powder is (2 to 2.4): 1.
in a more preferred embodiment, the mass ratio of carbon black to silicone powder is 2.2:1.
the carbon black is low Polycyclic Aromatic Hydrocarbon (PAH) carbon black, has very good dispersibility and can provide excellent extrusion performance for rubber materials.
The silicone powder is a porous natural microparticle, and is an inorganic mineral composed of natural quasi-spherical quartz and platy kaolin, and the minerals with different shapes are naturally combined to form a loose grain lamination mosaic structure, so that the silicone powder has ultrahigh fluidity and dispersibility.
In a more preferred embodiment, the silicone powder is purchased from Huffman silicone powder VM56, germany; the carbon black was purchased from SPHERON SO-LP, cabot corporation.
<Softening agent>
The softener is Sunpar paraffin base oil, and has excellent light stability and low volatility. The aromatic hydrocarbon content is low, so that the anti-oxidation and anti-fading performances are better.
In a preferred embodiment, the softener is a paraffinic oil SUNPAR P-116.
<Anti-aging agent>
The anti-aging agent is one or a combination of more than one of 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, 2-mercaptobenzimidazole and 2, 4-trimethyl-1, 2-dihydroquinoline polymer.
In a preferred embodiment, the anti-aging agent comprises 2-mercaptobenzimidazole and 4,4' -bis (α, α -dimethylbenzyl) diphenylamine.
In a more preferred embodiment, the mass ratio of 2-mercaptobenzimidazole to 4,4' -bis (α, α -dimethylbenzyl) diphenylamine is 1: (0.8-1.2).
In a more preferred embodiment, the mass ratio of 2-mercaptobenzimidazole to 4,4' -bis (α, α -dimethylbenzyl) diphenylamine is 1:1.
<active agent>
The active agent is one or a combination of more than one of zinc oxide, zinc stearate, calcium oxide, calcium chloride and barium chloride.
In a preferred embodiment, the active agent comprises zinc oxide and zinc stearate.
In a more preferred embodiment, the mass ratio of zinc oxide to zinc stearate is 4: (0.2-0.4).
In a more preferred embodiment, the mass ratio of zinc oxide to zinc stearate is 4:0.3.
the addition of zinc oxide and zinc stearate can reduce the dosage of the accelerator and improve the vulcanization speed of rubber.
<Heat conducting agent>
The heat conducting agent is active magnesium oxide.
In a preferred embodiment, the specific surface area of the activated magnesium oxide is 140 to 150m 2 /g; preferably, the specific surface area of the active magnesium oxide is 145m 2 /g。
In a more preferred embodiment, the activated magnesium oxide is purchased from Shanghai Neon materials technologies Co., ltd.
<Flow aid>
The flow aid is SINOHEAM FL001.
<Peroxide bridging agent>
The peroxide bridging agent is triallyl cyanurate.
In a preferred embodiment, the triallyl cyanurate is purchased from Rhenogran TAC-50 of the rhena chemistry.
<Peroxide curing agent>
The peroxide vulcanizing agent is selected from one or a combination of more of benzoyl peroxide, 2, 5-dimethyl-2, 5-di (benzoyl peroxide) hexane, tert-butyl peroxybenzoate, 1, 4-di-tert-butyl peroxydiisopropylbenzene, diisopropylbenzene peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane.
In a preferred embodiment, the peroxide curative is 1, 4-bis-t-butylperoxy diisopropylbenzene.
The ethylene propylene diene monomer is crosslinked by using organic peroxide, the organic peroxide is decomposed to generate alkyl free radicals under the action of heat, and the crosslinking reaction is initiated by abstracting hydrogen atoms on ethylene propylene rubber polymer chains, so that the decomposition speed is related to the degree of heating, the half life period is gradually shortened along with the rise of temperature, the decomposition speed is accelerated, carbon-carbon crosslinking bonds are formed among molecules under the action of the free radicals in a high-temperature rapid environment, the crosslinking bonds are highly stable, and the vulcanized rubber is endowed with very good chemical and physical stability.
According to the invention, through optimally designing an EPDM peroxidation vulcanization formula material, a Mooney viscosity value is selected to be 26-32, ethylene content is 45-56%, ethylene propylene diene monomer with 3.8-4.5% ethylidene norbornene content is selected to comprise carbon black and silicone powder as filler, 2-mercaptobenzimidazole and 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine are selected to be used as anti-aging agents, zinc oxide and zinc stearate are used as active agents, the respective contents are further controlled, under the action of a specific peroxide bridging agent, a peroxide vulcanizing agent and other components, the problems of thermal decomposition and oxidative destruction of rubber and thermal conductivity of a compounding agent at high temperature are solved, the fluidity and thermal conductivity of the material are improved, a mold cavity is rapidly filled, and the material is ensured to be rapidly and fully vulcanized in a high-temperature environment.
The second aspect of the invention provides a method for preparing a low-pressure-change EPDM sealing member capable of being rapidly peroxidized and vulcanized at high temperature, which at least comprises the following steps:
(1) Adding ethylene propylene diene monomer into an internal mixer, banburying, sequentially adding a filler, a softener, an active agent, an anti-aging agent, a heat conducting agent and a flow aid, banburying, discharging after uniform mixing, and cooling to obtain master batch;
(2) Putting the masterbatch into an open mill, adding a peroxide bridging agent and a peroxide vulcanizing agent, mixing, discharging sheets, and cooling by a cooling machine to obtain a final rubber sheet;
(3) Cutting the final rubber sheet into required model products, heating a die by a vacuum plate vulcanizing machine, putting the rubber sheet into a die cavity of the die to be matched with the die for primary vulcanization, and taking out a finished product after primary vulcanization;
(4) And (3) performing secondary vulcanization on the finished product, and obtaining the finished product after secondary vulcanization.
Examples
In order to better understand the above technical solution, the following describes the above technical solution in detail with reference to specific embodiments. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure. In addition, the raw materials used are commercially available unless otherwise indicated.
Example 1
The embodiment 1 of the invention provides a low-pressure-change EPDM sealing element capable of being rapidly peroxidized and vulcanized at high temperature, which comprises the following raw materials in percentage by weight: 35% of ethylene propylene diene monomer, 35% of filler, 5% of softener, 0.5% of anti-aging agent, 3.7% of active agent, 1% of heat conducting agent, 0.8% of flow aid, 0.4% of peroxide bridging agent and the balance of peroxide vulcanizing agent.
The ethylene propylene diene monomer was purchased from Arrheniaceae 2450, lanxess chemical Co., ltd.
The filler includes carbon black and silicone powder.
The mass ratio of the carbon black to the silicone powder is 2:1.
the silicone powder is purchased from Huffman silicone powder VM56, germany; the carbon black was purchased from SPHERON SO-LP, cabot corporation.
The softener is paraffin oil SUNPAR P-116.
The anti-aging agent includes 2-mercaptobenzimidazole and 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine.
The mass ratio of the 2-mercaptobenzimidazole to the 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine is 1:0.8.
the active agent includes zinc oxide and zinc stearate.
The mass ratio of the zinc oxide to the zinc stearate is 4:0.2.
the heat conducting agent is active magnesium oxide, and is purchased from Shendao magnesium oxide 150 of Shanghai Yi Yongxin materials science and technology Co.
The flow aid is SINOHAM FL001.
The peroxide bridging agent is triallyl cyanurate, rhenotran TAC-50 purchased from Rhenotran chemical.
The peroxide vulcanizing agent is 1, 4-di-tert-butyl peroxy diisopropylbenzene.
The preparation method of the low-pressure-variable EPDM sealing piece capable of being subjected to high-temperature rapid peroxidation and vulcanization comprises the following steps of:
(1) Adding ethylene propylene diene monomer into an internal mixer, banburying, sequentially adding a filler, a softener, an active agent, an anti-aging agent, a heat conducting agent and a flow aid, banburying, discharging after uniform mixing, and cooling to obtain master batch;
(2) Putting the masterbatch into an open mill, adding a peroxide bridging agent and a peroxide vulcanizing agent, mixing, discharging sheets, and cooling by a cooling machine to obtain a final rubber sheet;
(3) Cutting the final rubber sheet into required model products, heating a die by a vacuum plate vulcanizing machine, putting the rubber sheet into a die cavity of the die to be matched with the die for primary vulcanization, and taking out a finished product after primary vulcanization;
(4) And (3) performing secondary vulcanization on the finished product, and obtaining the finished product after secondary vulcanization.
Example 2
The embodiment 2 of the invention provides a low-pressure-change EPDM sealing member capable of being rapidly peroxidized and vulcanized at high temperature, which comprises the following raw materials in percentage by weight: 45% of ethylene propylene diene monomer rubber, 45% of filler, 10% of softener, 0.8% of anti-aging agent, 5% of active agent, 2% of heat conducting agent, 1.2% of flow aid, 0.6% of peroxide bridging agent and the balance of peroxide vulcanizing agent.
The ethylene propylene diene monomer was purchased from Arrheniaceae 2450, lanxess chemical Co., ltd.
The filler includes carbon black and silicone powder.
The mass ratio of the carbon black to the silicone powder is 2.4:1.
the silicone powder is purchased from Huffman silicone powder VM56, germany; the carbon black was purchased from SPHERON SO-LP, cabot corporation.
The softener is paraffin oil SUNPAR P-116.
The anti-aging agent includes 2-mercaptobenzimidazole and 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine.
The mass ratio of the 2-mercaptobenzimidazole to the 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine is 1:1.2.
the active agent includes zinc oxide and zinc stearate.
The mass ratio of the zinc oxide to the zinc stearate is 4:0.4.
the heat conducting agent is active magnesium oxide, and is purchased from Shendao magnesium oxide 150 of Shanghai Yi Yongxin materials science and technology Co.
The flow aid is SINOHAM FL001.
The peroxide bridging agent is triallyl cyanurate, rhenotran TAC-50 purchased from Rhenotran chemical.
The peroxide vulcanizing agent is 1, 4-di-tert-butyl peroxy diisopropylbenzene.
The preparation method of the low-pressure-variable EPDM sealing piece capable of being subjected to high-temperature rapid peroxidation and vulcanization comprises the following steps of:
(1) Adding ethylene propylene diene monomer into an internal mixer, banburying, sequentially adding a filler, a softener, an active agent, an anti-aging agent, a heat conducting agent and a flow aid, banburying, discharging after uniform mixing, and cooling to obtain master batch;
(2) Putting the masterbatch into an open mill, adding a peroxide bridging agent and a peroxide vulcanizing agent, mixing, discharging sheets, and cooling by a cooling machine to obtain a final rubber sheet;
(3) Cutting the final rubber sheet into required model products, heating a die by a vacuum plate vulcanizing machine, putting the rubber sheet into a die cavity of the die to be matched with the die for primary vulcanization, and taking out a finished product after primary vulcanization;
(4) And (3) performing secondary vulcanization on the finished product, and obtaining the finished product after secondary vulcanization.
Example 3
The embodiment 3 of the invention provides a low-pressure-change EPDM sealing member capable of being rapidly peroxidized and vulcanized at high temperature, which comprises the following raw materials in percentage by weight: 40% of ethylene propylene diene monomer rubber, 40% of filler, 7% of softener, 0.6% of anti-aging agent, 4.3% of active agent, 1.5% of heat conducting agent, 1% of flow aid, 0.5% of peroxide bridging agent and the balance of peroxide vulcanizing agent.
The ethylene propylene diene monomer was purchased from Arrheniaceae 2450, lanxess chemical Co., ltd.
The filler includes carbon black and silicone powder.
The mass ratio of the carbon black to the silicone powder is 2.2:1.
the silicone powder is purchased from Huffman silicone powder VM56, germany; the carbon black was purchased from SPHERON SO-LP, cabot corporation.
The softener is paraffin oil SUNPAR P-116.
The anti-aging agent includes 2-mercaptobenzimidazole and 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine.
The mass ratio of the 2-mercaptobenzimidazole to the 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine is 1:1.
the active agent includes zinc oxide and zinc stearate.
The mass ratio of the zinc oxide to the zinc stearate is 4:0.3.
the heat conducting agent is active magnesium oxide, and is purchased from Shendao magnesium oxide 150 of Shanghai Yi Yongxin materials science and technology Co.
The flow aid is SINOHAM FL001.
The peroxide bridging agent is triallyl cyanurate, rhenotran TAC-50 purchased from Rhenotran chemical.
The peroxide vulcanizing agent is 1, 4-di-tert-butyl peroxy diisopropylbenzene.
The preparation method of the low-pressure-variable EPDM sealing piece capable of being subjected to high-temperature rapid peroxidation and vulcanization comprises the following steps of:
(1) Adding ethylene propylene diene monomer into an internal mixer, banburying, sequentially adding a filler, a softener, an active agent, an anti-aging agent, a heat conducting agent and a flow aid, banburying, discharging after uniform mixing, and cooling to obtain master batch;
(2) Putting the masterbatch into an open mill, adding a peroxide bridging agent and a peroxide vulcanizing agent, mixing, discharging sheets, and cooling by a cooling machine to obtain a final rubber sheet;
(3) Cutting the final rubber sheet into required model products, heating a die by a vacuum plate vulcanizing machine, putting the rubber sheet into a die cavity of the die to be matched with the die for primary vulcanization, and taking out a finished product after primary vulcanization;
(4) And (3) performing secondary vulcanization on the finished product, and obtaining the finished product after secondary vulcanization.
Comparative example 1
Comparative example 1 of the present invention provides a low pressure change EPDM seal which is rapidly peroxidically vulcanizable at high temperature, the embodiment of which is the same as example 3, except that the ethylene propylene diene monomer has a mooney viscosity value of 24, wherein the ethylene content is 69%, the ethylidene norbornene content of the third monomer is 4.2%, and is purchased from aronew 2470, lanxess chemical company, germany.
Comparative example 2
Comparative example 2 of the present invention provides a low pressure change EPDM seal that can be rapidly peroxidically cured at high temperature, which is similar to example 3 in its specific embodiment, except that the ethylene propylene diene monomer has a mooney viscosity number of 51, wherein the ethylene content is 49%, the ethylidene norbornene content of the third monomer is 0%, and is purchased from arongo 3050, lanxess chemical company, germany.
Comparative example 3
Comparative example 3 of the present invention provides a low pressure change EPDM seal that can be rapidly peroxidically vulcanized at high temperature, the embodiment of which is the same as example 3, except that the mass ratio of carbon black to silicone powder is 2.2:2.
comparative example 4
Comparative example 4 of the present invention provides a low pressure change EPDM seal that can be rapidly peroxide cured at high temperature, the embodiment of which is the same as example 3 except that no silicone powder is present.
Comparative example 5
Comparative example 5 of the present invention provides a low pressure change EPDM seal that can be rapidly peroxide cured at high temperature, the embodiment of which is the same as example 3, except that the peroxide curative is replaced with sulfur.
Performance testing
The primary cure times of the above examples and comparative examples were recorded during the experiment;
the EPDM seals prepared in the above examples and comparative examples were subjected to a compression set test according to GB/T7759-2015 standard test method and 150 ℃ x 24H, respectively, and the compression set data was recorded.
TABLE 1
Figure BDA0002923596580000111
As can be seen from the data in the table, the EPDM sealing member prepared by the invention through the selection of the components and the content control can be vulcanized rapidly and fully in a high-temperature environment to improve the comprehensive performance of the product, especially the low-pressure denaturation performance, and the vulcanization time can be reduced.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.

Claims (8)

1. The low-pressure-change EPDM sealing member capable of being rapidly peroxidized and vulcanized at high temperature is characterized by comprising the following raw materials in percentage by weight: 35 to 45 percent of ethylene propylene diene monomer rubber, 35 to 45 percent of filler, 5 to 10 percent of softener, 0.5 to 0.8 percent of anti-aging agent, 3.7 to 5 percent of active agent, 1 to 2 percent of heat conducting agent, 0.8 to 1.2 percent of flow aid, 0.4 to 0.6 percent of peroxide bridging agent and the balance of peroxide vulcanizing agent;
the Mooney viscosity value of the ethylene propylene diene monomer is 26-32, wherein the ethylene content is 45-56%, and the ethylidene norbornene content of the third monomer is 3.8-4.5%;
the filler comprises carbon black and silicone powder; the mass ratio of the carbon black to the silicone powder is (2-2.4): 1.
2. the high temperature rapid peroxidized vulcanizable low pressure change EPDM seal of claim 1, wherein the anti-aging agent is selected from one or a combination of 4,4' -bis (α, α -dimethylbenzyl) diphenylamine, 2-mercaptobenzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer.
3. A high temperature rapid peroxidically vulcanizable low pressure change EPDM seal as claimed in claim 2, wherein the anti-aging agent includes 2-mercaptobenzimidazole and 4,4' -bis (α, α -dimethylbenzyl) diphenylamine; the mass ratio of the 2-mercaptobenzimidazole to the 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine is 1: (0.8-1.2).
4. The high temperature rapid peroxidized vulcanizable low pressure change EPDM seal as claimed in claim 1, wherein the active agent is selected from one or a combination of several of zinc oxide, zinc stearate, calcium oxide, calcium chloride, barium chloride.
5. The high temperature rapid peroxidized, low pressure change EPDM seal of claim 4, wherein said active agent includes zinc oxide and zinc stearate; the mass ratio of the zinc oxide to the zinc stearate is 4: (0.2-0.4).
6. The high temperature rapid peroxidized, low pressure change EPDM seal of claim 1, wherein said thermally conductive agent is activated magnesium oxide; the specific surface area of the active magnesium oxide is 140-150 m 2 /g。
7. The high temperature rapid peroxidized EPDM seal of claim 1, wherein the peroxide curative is selected from one or a combination of more of benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, t-butylperoxybenzoate, 1, 4-bis-t-butylperoxydiisopropylbenzene, diisopropylbenzene peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
8. Method for the preparation of a high temperature rapid peroxidically vulcanizable low pressure change EPDM seal as claimed in any one of claims 1 to 7, characterized in that it comprises at least the following steps:
adding ethylene propylene diene monomer into an internal mixer, banburying, sequentially adding a filler, a softener, an active agent, an anti-aging agent, a heat conducting agent and a flow aid, banburying, discharging after uniform mixing, and cooling to obtain master batch;
putting the masterbatch into an open mill, adding a peroxide bridging agent and a peroxide vulcanizing agent, mixing, discharging sheets, and cooling by a cooling machine to obtain a final rubber sheet;
cutting the final rubber sheet into required model products, heating a die by a vacuum plate vulcanizing machine, putting the rubber sheet into a die cavity of the die to be matched with the die for primary vulcanization, and taking out a finished product after primary vulcanization;
and (3) performing secondary vulcanization on the finished product, and obtaining the finished product after secondary vulcanization.
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