CN114801371B - Metal rubber composite board with high compression performance - Google Patents
Metal rubber composite board with high compression performance Download PDFInfo
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- CN114801371B CN114801371B CN202210582778.2A CN202210582778A CN114801371B CN 114801371 B CN114801371 B CN 114801371B CN 202210582778 A CN202210582778 A CN 202210582778A CN 114801371 B CN114801371 B CN 114801371B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/0288—Controlling heating or curing of polymers during moulding, e.g. by measuring temperatures or properties of the polymer and regulating the process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/73—Hydrophobic
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/14—Modified phenol-aldehyde condensates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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Abstract
The application relates to the field of sealing structural parts, and particularly discloses a metal rubber composite board with high compression performance. The metal rubber composite board comprises a metal substrate and an ethylene propylene diene monomer layer compounded on the surface of the metal substrate, wherein the ethylene propylene diene monomer layer comprises pretreated ethylene propylene diene monomer raw rubber, nitrile rubber raw rubber, sulfur, an alkyl phenolic resin cross-linking agent, an anti-aging agent, stearic acid, active zinc oxide, carbon black, naphthenic oil, organically modified montmorillonite and an accelerator EG-4; the preparation method comprises the following steps: firstly, carrying out surface treatment on a metal substrate, then preparing an ethylene propylene diene monomer layer through mixing and die casting, and finally compounding the ethylene propylene diene monomer layer on the surface of the metal substrate and then carrying out vulcanization treatment. The metal rubber composite board can be used as a rubber sealing piece, and has the advantages of good water repellency, oil repellency and sealing effect; in addition, the preparation method has the advantages of easy and uniform dispersion of the sizing material, simple vulcanization process, convenient adjustment and difficult frosting.
Description
Technical Field
The present application relates to the field of sealing structures, and more particularly, to a high compression performance metal rubber composite panel.
Background
Rubber seals are a general base element of the type used in sealing devices, and are mainly designed to solve the problems of leakage and poor sealing, and to play an important role in reducing leakage and environmental pollution. The rubber sealing element is a rubber product widely applied in the sealing technology, and meanwhile, the rubber product is prepared from an elastic high polymer material, so that the rubber product has a wider temperature range, and can generate larger deformation when being given with smaller stress in different media, and the deformation can provide contact pressure to compensate leakage clearance, thereby achieving the sealing purpose.
The rubber sealing piece is formed by cutting the metal glue spreading plate into a specific shape and installing the metal glue spreading plate at the pipeline connecting position, the vacuum instrument, the compressor sealing position and the valve sealing position, so that the sealing and leakage preventing functions are realized. The metal glue board is a metal composite material with a single-sided or double-sided surface coating, which is obtained by taking a metal plate as a base material, taking rubber as a basic film forming material, adding proper auxiliary agents, fillers, additives and the like, performing proper technological treatment and performing chemical crosslinking.
At present, the rubber sealing gasket is prepared by taking a stainless steel plate as a substrate and an ethylene propylene diene monomer rubber layer as a substrate coating, and is used as a compressor sealing gasket.
In view of the above related art, the applicant believes that although the ethylene propylene diene monomer has better ageing resistance and mechanical properties, in the preparation process, the ethylene propylene diene monomer is low in cohesive energy, and the sizing material is easy to bloom, so that the ethylene propylene diene monomer layer is easy to peel from the substrate, and the performance of the rubber sealing gasket is further reduced.
Disclosure of Invention
In order to solve the problems of low cohesive energy and low performance of a rubber sealing gasket caused by easy frosting of rubber materials in the related art, the application provides a metal rubber composite board with high compression performance.
The application provides a high compression performance's metal rubber composite sheet adopts following technical scheme:
the metal rubber composite board with high compression performance comprises a metal base material and ethylene propylene diene monomer rubber layers compounded on the upper surface and the lower surface of the metal base material, wherein the ethylene propylene diene monomer rubber layers are prepared from the following raw materials in parts by weight: 60-80 parts of pretreated ethylene propylene diene monomer rubber raw rubber, 10-20 parts of nitrile rubber raw rubber, 1-3 parts of sulfur, 4-8 parts of alkyl phenolic resin cross-linking agent, 0.1-0.3 part of anti-aging agent, 0.5-0.8 part of stearic acid, 0.1-0.3 part of active zinc oxide, 30-40 parts of carbon black, 20-30 parts of naphthenic oil, 2-5 parts of organically modified montmorillonite and 1-3 parts of accelerator EG-4; the pretreated ethylene propylene diene monomer rubber raw rubber is prepared by grafting ethylene propylene diene monomer rubber raw rubber with maleic anhydride.
By adopting the technical scheme, as the ethylene propylene diene monomer has good heat resistance, ozone resistance, ageing resistance and chemical stability, but the oil resistance and the bonding strength of the ethylene propylene diene monomer are lower, and the nitrile rubber has good oil resistance, wear resistance and bonding performance, but the ageing resistance and the heat resistance of the nitrile rubber are poorer, the comprehensive performance of an ethylene propylene diene monomer layer is improved by using the ethylene propylene diene monomer and the nitrile rubber in combination, meanwhile, the compatibility of the ethylene propylene diene monomer and the nitrile rubber is improved by modifying the ethylene propylene diene monomer, and the possibility that the sealing performance of a metal rubber composite plate is reduced due to uneven mixing of products is reduced.
Preferably, in the step S1, the ethylene content of the pretreated ethylene propylene diene monomer rubber raw rubber is 45wt.% to 60wt.%, the mooney viscosity of the ethylene propylene diene monomer rubber raw rubber is 50 to 70, the third monomer in the ethylene propylene diene monomer rubber raw rubber is ethylidene norbornene, and the mooney viscosity of the nitrile rubber raw rubber is 50 to 60.
By adopting the technical scheme, the ethylene content and the Mooney viscosity of the ethylene propylene diene monomer are regulated, so that the prepared ethylene propylene diene monomer has better elastic performance and mechanical property, meanwhile, the speed of a sulfur vulcanization system is improved by selecting the ethylene propylene diene monomer, and meanwhile, the vulcanization speed is improved by matching the sulfur vulcanization system and a resin vulcanization system, and the ethylene propylene diene monomer has the advantages of small odor, small environmental pollution, easiness in controlling the polymerization process and the like.
Preferably, the alkylphenol resin crosslinking agent comprises one or more of thermoplastic modified alkylphenol resins, p-tert-butylphenol formaldehyde resins and p-tert-octylphenol formaldehyde resins.
By adopting the technical scheme, the bonding performance and the heat resistance of the ethylene propylene diene monomer rubber layer system are further improved by selecting proper alkyl phenolic resin, the possibility of stripping the ethylene propylene diene monomer rubber layer is reduced, and the sealing performance of the rubber sealing gasket is further improved.
preferably,thealkylphenolicresincrosslinkingagentcomprisesthermoplasticmodifiedalkylphenolicresinandp-tert-octylphenolformaldehyderesin,whereinthethermoplasticmodifiedalkylphenolicresinismodifiedtackifyingresinCKM-A,andtheweightratioofthemodifiedtackifyingresinCKM-Atothep-tert-octylphenolformaldehyderesinis3: 1-2.
byadoptingthetechnicalscheme,themodifiedtackifyingresinCKM-Aandp-tert-octylphenolformaldehyderesinareselected,sothattheexcellentinitialviscosityoftherubbermaterialisendowed,thevulcanizingagentisalsousedforsupplementingthevulcanizingfunction,thesulfurvulcanizingsystemismatchedwiththeresinvulcanizingsystem,thecrosslinkingdensityisimproved,andthehardnessandtheelasticityofthepreparedethylenepropylenedienemonomerrubberlayerareexcellentthroughthedynamicadjustmentofthesulfurcontentandthecontentofthealkylphenolicresincrosslinkingagent,sothatthemodifiedethylenepropylenedienemonomerrubberismoresuitableforarubbersealinggasketsystem.
Preferably, the anti-aging agent comprises an anti-aging agent MMBZ and an anti-aging agent HS-911, wherein the weight ratio of the anti-aging agent MMBZ to the anti-aging agent HS-911 is 4:1-2.
By adopting the technical scheme, the heat-resistant and oxygen-aging performance of the nitrile rubber in the ethylene propylene diene monomer layer is improved by the collaborative use of the anti-aging agent MMBZ anti-aging agent HS-911, and meanwhile, the performance of the nitrile rubber is improved by the mixed use of the ethylene propylene diene monomer and the nitrile rubber, and the use amount of the anti-aging agent is effectively reduced, so that the cost is saved.
Preferably, the organically modified montmorillonite is prepared by modifying the surface of montmorillonite by octadecyl methyl diethyl quaternary ammonium salt, and the particle size of the organically modified montmorillonite is 10-20 mu m.
By adopting the technical scheme, cations are attached to silicate sheets and organic parts are remained between layers by carrying out surface modification on montmorillonite, so that the interlayer distance is increased, the interlayer microenvironment is improved, an intercalation type nano composite structure is further formed, and the thermo-oxidative aging resistance, the water resistance and the oil permeation resistance of the ethylene propylene diene monomer layer are further improved.
Preferably, the preparation of the metal rubber composite board comprises the following steps:
s1, preparing raw materials;
s2, treating the surface of the metal substrate;
s3, rubber mixing to obtain a rubber mixed film;
s4, vulcanization molding, namely adhering the rubber compound film in the step S3 to the upper surface and the lower surface of the metal substrate subjected to surface treatment in the step S2, adjusting the vulcanization temperature to be 150-160 ℃ and the vulcanization time to be 30-40min, wherein the pressure born by the metal rubber composite board is 1-5MPa, and standing for 1-2h at room temperature after vulcanization to obtain the finished metal rubber composite board.
Through adopting above-mentioned technical scheme, through the mode of mixing earlier and then vulcanizing, through exerting force to rubber compound film and metal substrate when vulcanizing to improved the bonding strength of metal substrate and ethylene propylene diene monomer rubber layer, simultaneously, owing to carried out surface treatment to metal substrate, more be favorable to rubber compound film and metal substrate to compound.
Preferably, the step S2 of surface treatment of the metal substrate comprises the following steps:
s2.1, degreasing and frosting the surface of the metal substrate;
s2.2, uniformly mixing a silane coupling agent KBM-403, glycerol and deionized water to ensure that the silane coupling agent KBM-403 is prehydrolyzed to prepare a silane solution;
and S3.3, uniformly spraying the silane solution prepared in the step S2.2 on the outer wall of the metal substrate in the step S2.1.
Through adopting above-mentioned technical scheme, through making silane coupling agent prehydrolysis, can produce compact hydrophobic membrane between the hydroalcoholic hydroxyl, simultaneously, the hydrophobic membrane that forms can take place the reaction with phenolic resin, further improved the bonding strength of metal substrate and EPDM layer.
Preferably, the step S3 rubber mixing comprises the following steps:
s3.1, regulating the initial temperature to be 90-100 ℃, increasing the temperature at the speed of 10-15 ℃/min, adding pretreated ethylene propylene diene monomer rubber raw rubber and nitrile rubber raw rubber, sequentially adding active zinc oxide, organically modified montmorillonite, carbon black, naphthenic oil and stearic acid, and uniformly mixing;
s3.2, adding an anti-aging agent into the step S3.1, and uniformly mixing until the temperature is 150 ℃ or the time is 5min, and discharging the rubber;
s3.3, thinning the sizing material discharged in the step S3.2 for 2-4 times, and cooling the thinned sizing material to room temperature;
s3.4, placing the 1/3-1/2 sizing material in the step S3.3 at the temperature of 35-45 ℃, sequentially adding the accelerator EG-4, sulfur, the alkyl phenolic resin cross-linking agent and the rest sizing material, mixing, heating at the speed of 35-45 ℃/min until the temperature is increased to 110 ℃ or the mixing time is 2min, and discharging the sizing material.
By adopting the technical scheme, the sulfur vulcanizing system is matched with the resin vulcanizing system, so that sulfur can be added in the second-stage vulcanizing process while the sulfur consumption is reduced in the ethylene propylene diene monomer rubber system, the problem of difficult sulfur dispersion is avoided, and meanwhile, the possibility of frosting caused by uneven material dispersion in the ethylene propylene diene monomer rubber layer system is further reduced by adjusting the material adding sequence of the ethylene propylene diene monomer rubber layer system.
Preferably, the preparation of the pretreated ethylene propylene diene monomer rubber raw rubber comprises the following steps:
t1, preparing raw ethylene propylene diene monomer rubber serving as a raw material;
t2, uniformly mixing ethylene propylene diene monomer rubber, maleic anhydride and benzoyl peroxide in the step T1, raising the temperature to 170-180 ℃, reacting for 10-15min, extruding, and granulating, wherein the mass ratio of the ethylene propylene diene monomer rubber, the maleic anhydride and the benzoyl peroxide is 10:1-3:0.5;
and T3, vacuum drying the ethylene propylene diene monomer rubber raw rubber granulated in the step T2 at the drying temperature of 55-75 ℃ for 6-8 hours to obtain the pretreated ethylene propylene diene monomer rubber raw rubber.
By adopting the technical scheme, as the maleic anhydride has good compatibility with the nitrile rubber, and the maleic anhydride is adopted to modify the ethylene propylene diene monomer rubber, the problem of poor compatibility of ethylene propylene diene monomer rubber raw rubber and nitrile rubber raw rubber is solved, the strength of an ethylene propylene diene monomer rubber layer is improved, and the problem of glue stock frosting caused by poor compatibility of the ethylene propylene diene monomer rubber raw rubber and the nitrile rubber raw rubber is solved.
In summary, the present application has the following beneficial effects:
1. the ethylene propylene diene monomer rubber layer is prepared by mixing ethylene propylene diene monomer rubber raw rubber and nitrile rubber raw rubber, and the ethylene propylene diene monomer rubber raw rubber is modified, so that the compatibility of the ethylene propylene diene monomer rubber raw rubber and the nitrile rubber is improved, and meanwhile, the characteristics of the ethylene propylene diene monomer rubber raw rubber and the nitrile rubber are mutually supplemented, so that the ozone resistance, ageing resistance and bonding performance of the metal rubber composite plate are improved;
2. the alkyl phenolic resin preferably adopted in the application not only can be used for tackifying an ethylene propylene diene monomer rubber layer, but also can be used as a vulcanizing agent, and the strength of the three-dimensional crosslinked reticular structure is improved through mutual complementation of sulfur vulcanization and resin vulcanization, and meanwhile, the consumption of sulfur is reduced through dynamic adjustment of the sulfur and the alkyl phenolic resin, and the frosting phenomenon caused by difficult sulfur dispersion is reduced;
3. according to the preparation method, the metal substrate is subjected to surface treatment, so that the oleophobic and hydrophobic properties of the surface of the metal substrate are improved, silane can be crosslinked with phenolic resin after being hydrolyzed, and the strength of the ethylene propylene diene monomer rubber layer is further improved.
Detailed Description
Examples of preparation of starting materials and/or intermediates
Table 1 shows the starting materials and CAS numbers used in the present application
| Raw materials | CAS number |
| Stearic acid | 57-11-4 |
| Active zinc oxide | 1314-13-2 |
| Carbon black | 1333-86-4 |
The model of the naphthenic oil is naphthenic oil N4006;
the model of the carbon black is carbon black N660;
the brand of polylactic acid is REVODE190;
the silane coupling agent is selected from silane coupling agent KBM-403
The organic modified montmorillonite has the brand of I.34TCN and the volume density of 250-300Kg/m 3 The grain diameter is 14-18 mu m;
the ethylene propylene diene monomer rubber is EPDM4095, the ethylene content is 54wt.%, the Mooney viscosity ML (1+4) is 59 at 125 ℃, and the ethylidene norbornene content of the third monomer is 8.1wt.%;
the nitrile rubber is NBR3305E, and the Mooney viscosity ML (1+4) at 100deg.C is 55.
Preparation example 1, preparation of pretreated ethylene propylene diene monomer rubber raw rubber, comprises the following steps:
t1, preparing raw ethylene propylene diene monomer rubber serving as a raw material;
t2, feeding 1kg of ethylene propylene diene monomer rubber raw rubber in the step T1, 0.2kg of maleic anhydride and 0.05kg of benzoyl peroxide into a double-screw extruder, uniformly mixing, raising the temperature to 180 ℃, reacting for 10min, extruding, granulating the extruded material by a granulator, wherein the granularity of the extruded material is 4 (+ -1.5) mm;
and T3, vacuum drying the ethylene propylene diene monomer rubber raw rubber granulated in the step T2 at the drying temperature of 75 ℃ for 6 hours to obtain the pretreated ethylene propylene diene monomer rubber raw rubber.
Examples
Example 1
The utility model provides a high compression performance's metal rubber composite sheet, includes metal substrate and the ethylene propylene diene monomer layer of compounding in metal substrate upper and lower surface, and wherein, the material that metal substrate selected is cold-rolled steel sheet, and cold-rolled steel sheet's thickness is 1mm, and the thickness of the ethylene propylene diene monomer layer that adopts is 0.5mm.
theethylenepropylenedienemonomerrubberlayerispreparedfrom60gofpretreatedethylenepropylenedienemonomerrubber,15gofnitrilerubber,2gofsulfur,2.6gofmodifiedtackifyingresinCKM-A,1.3gofp-tert-octylphenolformaldehyderesin,0.145gofantioxidantMMBZ,0.054gofantioxidantHS-911,0.7gofstearicacid,0.2gofactivezincoxide,35gofcarbonblack,25gofnaphthenicoil,2goforganicallymodifiedmontmorilloniteand2gofacceleratorEG-4.
The preparation of the metal rubber composite board with high compression performance comprises the following steps:
s1, preparing raw materials;
s2, treating the surface of the metal substrate;
s2.1, immersing a metal substrate in an alkali cleaning solution heated to 100 ℃ for degreasing and deoiling treatment, wherein the alkali cleaning solution can be low-foam alkali metal cleaning agent PC-102, washing and drying the metal substrate by using clear water, polishing the surface of the metal substrate by using a grinding wheel after drying, washing and drying the metal substrate by using clear water again;
s3, rubber mixing;
s3.1, mixing by adopting an internal mixer, adjusting the initial temperature of the internal mixer to be 100 ℃, raising the temperature at the speed of 10 ℃/min, adding 60g of pretreated ethylene propylene diene monomer rubber raw rubber (ethylene propylene diene monomer rubber raw rubber prepared in preparation example 1), 15g of nitrile rubber raw rubber, sequentially adding 0.2g of active zinc oxide, 2g of organically modified montmorillonite, 35g of carbon black, 25g of naphthenic oil and 0.7g of stearic acid, mixing uniformly, and adjusting the rotating speed to be 77r/min;
s3.2, adding 0.145g of an anti-aging agent MMBZ and 0.054g of an anti-aging agent HS-911 into the step S3.1, uniformly mixing, and discharging rubber until the temperature is 150 ℃ or the time is 5 min;
s3.3, thinly passing the sizing material discharged in the step S3.2 on an open mill with the temperature of the roll being 50 ℃ for 2-4 times, adjusting the roll spacing to be 2.5mm, checking, and cooling the qualified thinly passed sizing material to room temperature;
S3.4,regulatingthetemperatureoftheinternalmixerto40℃andtherotatingspeedto77r/min,sequentiallyadding1/2ofthesizingmaterialinthestepS3.3,2gofacceleratorEG-4,2gofsulfur,2.6gofmodifiedtackifyingresinCKM-A,1.3gofp-tert-octylphenolformaldehyderesinand1/2ofthesizingmaterialinthestepS3.3intotheinternalmixer,heatingatthespeedof35℃/minwhileaddinguntilthetemperaturerisesto110℃orthemixingtimeis2min,anddischargingthesizingmaterial.
S4, vulcanization molding, namely adhering the rubber compound film in the step S3.4 to the upper and lower surfaces of the metal substrate subjected to the surface treatment in the step S2, then placing the metal substrate on a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization time is 40min, the pressure born by the metal rubber composite part is 2MPa, and standing for 2 hours at room temperature after vulcanization to obtain the finished metal rubber composite plate.
Example 2, example 2 differs from example 1 in that: the pretreated ethylene propylene diene monomer rubber added in the step S3.1 is 80g.
Example 3, example 3 differs from example 1 in that: the pretreated ethylene propylene diene monomer rubber added in the step S3.1 is 70g.
Example 4, example 4 differs from example 3 in that the metal substrate surface treatment further comprises the steps of:
s2.2, uniformly mixing a silane coupling agent KBM-403, glycerol and deionized water to ensure that the silane coupling agent KBM-403 is prehydrolyzed to prepare a silane solution;
and S3.3, uniformly spraying the silane solution prepared in the step S2.2 on the outer wall of the metal substrate in the step S2.1.
Example 5, example 5 differs from example 4 in that: themodifiedtackifyingresinCKM-AinstepS3.4was4g,andp-tert-octylphenolformaldehyderesinwas2g.
Example 6, example 6 differs from example 4 in that: themodifiedtackifyingresinCKM-AinstepS4.3was5.33g,andp-tert-octylphenolformaldehyderesinwas2.67g.
Example 7, example 7 differs from example 5 in that: the organically modified montmorillonite used in step S3.1 was 3.5g.
Example 8, example 8 differs from example 5 in that: the organic modified montmorillonite adopted in the step S3.1 is 5g.
Comparative example
Comparative example 1 differs from example 1 in that: the pretreated ethylene propylene diene monomer rubber added in the step S3.1 is 50g.
Comparative example 2 differs from example 1 in that: the pretreated ethylene propylene diene monomer rubber added in the step S3.1 is 90g.
Comparative example 3 differs from comparative example 1 in that: the ethylene propylene diene monomer rubber raw rubber adopted in the step S3.1 is not pretreated.
Comparative example 4 differs from example 4 in that: themodifiedtackifyingresinCKM-AinstepS3.4was1.33g,andp-tert-octylphenolformaldehyderesinwas0.67g.
Comparative example 5 differs from example 6 in that: themodifiedtackifyingresinCKM-AinstepS3.4was6.67g,andp-tert-octylphenolformaldehyderesinwas3.33g.
Comparative example 6 differs from example 7 in that: in the step S3.1, 1g of organically modified montmorillonite is adopted.
Comparative example 7 differs from example 7 in that: in the step S3.1, organic modified montmorillonite is adopted to be 6g.
Comparative example 8 differs from comparative example 6 in that: the montmorillonite used in the step S3.1 is not subjected to surface modification treatment.
Performance test
Compression spring rate test: the compression rate and the rebound rate are measured according to GB/T20671.2-2006 test method for compression rate rebound rate of gasket materials.
And (3) sealing performance test: the tightness was measured according to GB/T20671.4-2006 method for tightness test of gasket Material.
Oil resistance test: the weight and thickness change rates were measured with IRM903 oil at 150℃for 5h according to ASTM F-36.
Impact resistance test: according to GB/T1732-2020 "impact resistance measurement method of paint film", the phenomena of cracks, wrinkles and flaking are observed.
Detection method/test method
Table 2 is the performance test data of the examples of the present application
Table 3 shows the performance test data of the comparative examples of the present application
It can be seen from the combination of examples 1 to 3 and comparative examples 1 to 2 and tables 2 and 3 that the effect is better when the content of the pretreated ethylene propylene diene monomer rubber raw rubber is 60 to 80 parts, and the performance improvement is smaller when the content of the pretreated ethylene propylene diene monomer rubber raw rubber is increased from 70 parts to 80 parts. When the content of the pretreated ethylene propylene diene monomer rubber raw rubber is less than 60 parts, the performance of the pretreated ethylene propylene diene monomer rubber raw rubber is greatly reduced due to the fact that the content of the pretreated ethylene propylene diene monomer rubber raw rubber is too low, and meanwhile, the performance of the metal rubber composite board is also greatly reduced when the content of the pretreated ethylene propylene diene monomer rubber raw rubber is too high.
It can be seen from the combination of comparative examples 1 and 3 and the combination of table 3 that by modifying the ethylene propylene diene monomer rubber, the compatibility of the ethylene propylene diene monomer rubber and the nitrile rubber is improved, and the performance of the ethylene propylene diene monomer rubber layer is further improved.
It can be seen from the combination of examples 3 and 4 and table 2 that the impact strength of the metal rubber composite plate is improved by treating the surface of the metal substrate, in which the silane treated on the surface of the metal can be crosslinked with the phenolic resin, although the elasticity and compression properties of the ethylene propylene diene monomer rubber layer are not greatly changed.
It can be seen from the combination of examples 4 to 6 and comparative examples 4 and 5 and the combination of tables 2 and 3 that the effect is excellent by adjusting the content of the alkylphenol-formaldehyde resin crosslinking agent, and that the effect is excellent when the content of the alkylphenol-formaldehyde resin crosslinking agent is 4 to 8 parts, and that the effect is excellent when the content of the alkylphenol-formaldehyde resin crosslinking agent is 6 parts.
It can be seen from the combination of examples 5, 7, 8 and comparative examples 6 and 7 and the combination of tables 2 and 3 that the effect is better by adjusting the content of the organically modified montmorillonite, and when the part of the organically modified montmorillonite is 2 to 5, especially when the content of the organically modified montmorillonite is 3.5 parts, the effect is best, and the performance of the metal rubber composite board is affected by the excessively high or excessively low content of the organically modified montmorillonite.
It can be seen from the combination of comparative examples 6 and 8 and the combination of table 3 that the interlayer structure of montmorillonite is increased by modifying the montmorillonite, so that the performance of the metal rubber composite board is further improved.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (6)
1. The metal rubber composite board with high compression performance is characterized by comprising a metal base material and ethylene propylene diene monomer rubber layers compounded on the upper surface and the lower surface of the metal base material, wherein the ethylene propylene diene monomer rubber layers are prepared from the following raw materials in parts by weight: 60-80 parts of pretreated ethylene propylene diene monomer rubber raw rubber, 10-20 parts of nitrile rubber raw rubber, 1-3 parts of sulfur, 4-8 parts of alkyl phenolic resin cross-linking agent, 0.1-0.3 part of anti-aging agent, 0.5-0.8 part of stearic acid, 0.1-0.3 part of active zinc oxide, 30-40 parts of carbon black, 20-30 parts of naphthenic oil, 2-5 parts of organically modified montmorillonite and 1-3 parts of accelerator EG-4; the pretreated ethylene propylene diene monomer rubber raw rubber is prepared by grafting ethylene propylene diene monomer rubber raw rubber with maleic anhydride; thealkylphenolicresincrosslinkingagentcomprisesthermoplasticmodifiedalkylphenolicresinandp-tert-octylphenolformaldehyderesin,whereinthethermoplasticmodifiedalkylphenolicresinismodifiedtackifyingresinCKM-A,andtheweightratioofthemodifiedtackifyingresinCKM-Atothep-tert-octylphenolformaldehyderesinis3: 1-2; the preparation of the metal rubber composite board comprises the following steps:
s1, preparing raw materials;
s2, treating the surface of the metal substrate;
s3, rubber mixing to obtain a rubber mixed film;
s4, vulcanization molding, namely adhering the rubber compound film in the step S3 to the upper surface and the lower surface of the metal substrate subjected to surface treatment in the step S2, adjusting the vulcanization temperature to be 150-160 ℃ and the vulcanization time to be 30-40min, wherein the pressure born by the metal rubber composite board is 1-5MPa, and standing for 1-2h at room temperature after vulcanization to obtain a finished metal rubber composite board; step S2, surface treatment of the metal substrate, comprising the following steps:
s2.1, degreasing and frosting the surface of the metal substrate;
s2.2, uniformly mixing a silane coupling agent KBM-403, glycerol and deionized water to ensure that the silane coupling agent KBM-403 is prehydrolyzed to prepare a silane solution;
and S3.3, uniformly spraying the silane solution prepared in the step S2.2 on the outer wall of the metal substrate in the step S2.1.
2. The high compression performance metal rubber composite plate of claim 1, wherein: the ethylene content of the pretreated ethylene propylene diene monomer rubber raw rubber in the step S1 is 45-60 wt%, the Mooney viscosity of the ethylene propylene diene monomer rubber raw rubber is 50-70, the third monomer in the ethylene propylene diene monomer rubber raw rubber is ethylidene norbornene, and the Mooney viscosity of the nitrile rubber raw rubber is 50-60.
3. The high compression performance metal rubber composite plate of claim 1, wherein: the anti-aging agent comprises an anti-aging agent MMBZ and an anti-aging agent HS-911, wherein the weight ratio of the anti-aging agent MMBZ to the anti-aging agent HS-911 is 4:1-2.
4. The high compression performance metal rubber composite plate of claim 1, wherein: the organic modified montmorillonite is prepared by modifying the surface of montmorillonite by octadecyl methyl diethyl quaternary ammonium salt, and the particle size of the organic modified montmorillonite is 10-20 mu m.
5. The high-compression-performance metal rubber composite board according to claim 4, wherein the rubber mixing in the step S3 comprises the following steps:
s3.1, regulating the initial temperature to be 90-100 ℃, increasing the temperature at the speed of 10-15 ℃/min, adding pretreated ethylene propylene diene monomer rubber raw rubber and nitrile rubber raw rubber, sequentially adding active zinc oxide, organically modified montmorillonite, carbon black, naphthenic oil and stearic acid, and uniformly mixing;
s3.2, adding an anti-aging agent into the step S3.1, and uniformly mixing until the temperature is 150 ℃ or the time is 5min, and discharging the rubber;
s3.3, thinning the sizing material discharged in the step S3.2 for 2-4 times, and cooling the thinned sizing material to room temperature;
s3.4, placing the 1/3-1/2 sizing material in the step S3.3 at the temperature of 35-45 ℃, sequentially adding the accelerator EG-4, sulfur, the alkyl phenolic resin cross-linking agent and the rest sizing material, mixing, heating at the speed of 35-45 ℃/min while mixing until the temperature is increased to 110 ℃ or the mixing time is 2min, and discharging the sizing material.
6. The high-compression-performance metal rubber composite board according to claim 1, wherein the preparation of the pretreated ethylene propylene diene monomer rubber raw rubber comprises the following steps:
t1, preparing raw ethylene propylene diene monomer rubber serving as a raw material;
t2, uniformly mixing ethylene propylene diene monomer rubber, maleic anhydride and benzoyl peroxide in the step T1, raising the temperature to 170-180 ℃, reacting for 10-15min, extruding, and granulating, wherein the mass ratio of the ethylene propylene diene monomer rubber, the maleic anhydride and the benzoyl peroxide is 10:1-3:0.5;
and T3, vacuum drying the ethylene propylene diene monomer rubber raw rubber granulated in the step T2 at the drying temperature of 55-75 ℃ for 6-8 hours to obtain the pretreated ethylene propylene diene monomer rubber raw rubber.
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| CN1425712A (en) * | 2003-01-09 | 2003-06-25 | 上海交通大学 | Triple ethylene-propylene rubber/montmorillonoid peeling nano composite material and its preparing method |
| CN103483642A (en) * | 2013-09-30 | 2014-01-01 | 深圳市科聚新材料有限公司 | Nitrile rubber/ethylene propylene diene monomer ageing-resistant material and preparation method thereof |
| CN110396252A (en) * | 2018-04-24 | 2019-11-01 | 中国石油化工股份有限公司 | The preparation method of nanocomposite and the preparation method of vulcanized rubber |
| CN114426709A (en) * | 2020-10-09 | 2022-05-03 | 中国石油化工股份有限公司 | Rubber composition based on nitrile rubber and ethylene propylene diene monomer, application of rubber composition, vulcanized rubber, preparation method of vulcanized rubber and application of vulcanized rubber |
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| US10047251B2 (en) * | 2013-04-23 | 2018-08-14 | The Yokohama Rubber Co., Ltd. | Rubber composition adhesive to metal surface, laminated body of rubber composition and metal, vulcanized rubber product, and method of producing vulcanized rubber product |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425712A (en) * | 2003-01-09 | 2003-06-25 | 上海交通大学 | Triple ethylene-propylene rubber/montmorillonoid peeling nano composite material and its preparing method |
| CN103483642A (en) * | 2013-09-30 | 2014-01-01 | 深圳市科聚新材料有限公司 | Nitrile rubber/ethylene propylene diene monomer ageing-resistant material and preparation method thereof |
| CN110396252A (en) * | 2018-04-24 | 2019-11-01 | 中国石油化工股份有限公司 | The preparation method of nanocomposite and the preparation method of vulcanized rubber |
| CN114426709A (en) * | 2020-10-09 | 2022-05-03 | 中国石油化工股份有限公司 | Rubber composition based on nitrile rubber and ethylene propylene diene monomer, application of rubber composition, vulcanized rubber, preparation method of vulcanized rubber and application of vulcanized rubber |
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