CN106752403B - A kind of foaming nitrile rubber composite metal plate and preparation method thereof - Google Patents
A kind of foaming nitrile rubber composite metal plate and preparation method thereof Download PDFInfo
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- CN106752403B CN106752403B CN201611125219.XA CN201611125219A CN106752403B CN 106752403 B CN106752403 B CN 106752403B CN 201611125219 A CN201611125219 A CN 201611125219A CN 106752403 B CN106752403 B CN 106752403B
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- Prior art keywords
- foaming
- nitrile rubber
- parts
- agent
- metal substrate
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 73
- 239000002184 metal Substances 0.000 title claims abstract description 73
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 63
- 238000005187 foaming Methods 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 48
- 239000005060 rubber Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004088 foaming agent Substances 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000005864 Sulphur Substances 0.000 claims abstract description 19
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 19
- 230000003712 anti-aging effect Effects 0.000 claims description 13
- 238000004073 vulcanization Methods 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 229920001661 Chitosan Polymers 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 239000004156 Azodicarbonamide Substances 0.000 claims description 7
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 7
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 7
- 238000007761 roller coating Methods 0.000 claims description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- 229960002447 thiram Drugs 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 claims 1
- 230000006835 compression Effects 0.000 abstract description 10
- 238000007906 compression Methods 0.000 abstract description 10
- 239000003921 oil Substances 0.000 abstract description 10
- 230000004584 weight gain Effects 0.000 abstract description 5
- 235000019786 weight gain Nutrition 0.000 abstract description 5
- -1 thicken < 3% Substances 0.000 abstract description 4
- 239000000295 fuel oil Substances 0.000 abstract description 3
- 239000003566 sealing material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010073 coating (rubber) Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000011120 plywood Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013527 degreasing agent Substances 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920001967 Metal rubber Polymers 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- ACOGMWBDRJJKNB-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.CC(O)=O ACOGMWBDRJJKNB-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/02—Copolymers with acrylonitrile
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of foaming nitrile rubber composite metal plates and preparation method thereof, are related to sealing material.A kind of foaming nitrile rubber composite metal plate, including metal substrate, foaming rubber layer is arranged in the surface of the metal substrate, and the foaming rubber layer is made of the raw material of following mass parts: 100 parts of nitrile rubber, 1 ~ 10 part of zinc oxide, 2 ~ 10 parts of promotor, 0.5 ~ 5 part of sulphur, 20 ~ 40 parts of carbon black, 1 ~ 5 part of foaming agent, 1 ~ 10 part of auxiliary agent.The compression ratio that the present invention develops foaming nitrile rubber composite metal plate is 32 ~ 47%, rebound degree > 80%, creep relaxation rate < 4%, leakproofness ml/hr≤0.02, oil seal No leakage, 5 hours weight gain < 2% of the B of resistance to fuel oil room temperature, thicken < 4%, 150 DEG C of 5h weight gain < 4% of resistance to ASTM3 oil, thicken < 3%, composite plate of the present invention shows excellent compression ratio, rebound degree, creep-resistant property and heatproof oil resistance etc..
Description
Technical field
The invention belongs to sealing material technical field, in particular to a kind of foaming nitrile rubber composite metal plate and its preparation
Method.
Background technique
Nitrile rubber (NBR) has excellent oil resistant, solvent resistant and heat resistance because having itrile group in molecule, by matching
Nitrile rubber after conjunction can have good compression resilience, and long-term use temperature can reach 150 DEG C.And it is best with heat resistance
Fluorubber is compared, and price is only the 1/5 of the latter, has apparent cost advantage.But simultaneously because the presence of double bond makes butyronitrile
Rubber resistance to ag(e)ing, oxidative resistance are not so good as other saturated rubbers.
By the nitrile rubber coating of nitrile rubber raw rubber and compounding agent preparation, coated using modes such as spraying, roller coating, showerings
Nitrile rubber coating gasket seal is obtained after metallic substrate surface, vulcanization, molding.Since current automobile engine is general at present
All over water cooling mode is used, cylinder seal gasket is other than the annulus of very little near engine cylinder mouth, other position work temperature
Generally below 140 DEG C of degree, therefore the nitrile rubber coating through special compounding, entirely possible substitution fluororubber coating reach automobile
Engine seal request, to substantially reduce cost, therefore, it is necessary to study the nitrile rubbers of exploitation automobile engine sealing
Coating and its construction technology.
Application No. is 201510045730.8 patents to disclose a kind of preparation method of nitrile rubber composite metal plate, institute
The raw material for stating recovery processing technique include nitrile rubber, zinc oxide, stearic acid, sublimed sulfur, carbon black, two fourth of phthalic acid
Ester, butyl acetate, bentonite, Kaimoluoke and cetyl trimethylammonium bromide, the preparation method include the following steps: (1)
It crushes, takes one, 1000ml beaker, weigh 100g nitrile rubber on an electronic balance, the omnipotent crushing of high speed is put into after being cut into small pieces
It is crushed in machine.(2) then stirring and dissolving is dissolved with 500ml butyl acetate, electric mixing is carried out in course of dissolution
It mixes, revolving speed 70r/min, rubber master batch is uniform after stirring several hours.It is the high resiliency of the existing rubber elastomer of the composite material, excellent
Compressibility, but also with the high intensity of metal core board, therefore have excellent sealing performance and antivibration, heat resistance, can be not
With occasion play protection, sealing, shock resistance, vibration damping, it is heat-resisting the effects of, especially its structure and excellent leakproofness, make its
The field of sealing technology such as motor vehicle have been widely used.Application No. is 201610506263 patents to disclose a kind of metal rubber and plastic
Foaming composite board, including metal base, the surface of the metal base are successively attached with the 1st adhesive phase, the 2nd adhesive phase
And rubber layer.The rubber layer is made of the raw material of following parts by weight: 100 parts of rubber, ethylene ~ acetate ethylene copolymer 20 ~
30 parts, 10 ~ 20 parts of activating agent, foaming 10 ~ 20 parts of rubber powder, foaming promote 3 ~ 10 parts of agent, 8 ~ 20 parts of foaming system, 40 ~ 80 parts of filler,
3 ~ 10 parts of softening agent, 3 ~ 8 parts of vulcanizing system, 1 ~ 2 part of levelling agent, 2 ~ 3 parts of defoaming agent；1st adhesive phase is by following weight
The raw material of number is made: 10 ~ 15 parts of vinyl silicane coupling agent, 75 ~ 85 parts of methanol, 1 ~ 2 part of hydrochloric acid, 10 ~ 20 parts of water；Described
2 adhesive phases are made of the raw material of following parts by weight: 30 ~ 40 parts of thermosetting resin, 75 ~ 85 parts of methanol.The invention by
By rubber and EVA and for making up the shortcomings that rubber product is easy aging in rubber layer, obtained rubber and plastic composite layer was both maintained
The plasticity of EVA material possesses the softness, elasticity, anti-skidding and excellent abrasion resistance of rubber material again.Above-mentioned blown rubber is multiple
Plywood material is used equally for field of sealing technology, but compression, resilience performance and its creep resisting ability of above-mentioned composite plate need into one
Step improves and reinforces.
Summary of the invention
In view of this, technical problem to be solved by the invention is to provide a kind of foaming nitrile rubber composite metal plate, with
For the sealing of automobile, motorcycle, industrial sewing machine etc., to improve its compression performance and resilience performance, while enhance its resist it is compacted
Become slack ability.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of foaming nitrile rubber composite metal plate, including metal substrate, the surface setting foaming rubber of the metal substrate
Glue-line, the foaming rubber layer are made of the raw material of following mass parts: 100 parts of nitrile rubber, 1 ~ 10 part of zinc oxide, promotor 2 ~
10 parts, 0.5 ~ 5 part of sulphur, 20 ~ 40 parts of carbon black, 1 ~ 5 part of foaming agent, 1 ~ 10 part of auxiliary agent.
Preferably, the foaming agent is azodicarbonamide and/or CR-4305, the azodicarbonamide and CR-4305
Weight ratio be 1:2 ~ 3.
Preferably, the promotor is thuriam acceserator or/and sulfenamide type accelerators.
Preferably, the promotor be tetramethylthiuram disulfide and N- cyclohexyl -2-[4-morpholinodithio sulfenamide, two
The weight ratio of person is 0.8 ~ 1:1.
Preferably, the auxiliary agent is chitosan derivatives and/or anti-aging agent.
Preferably, the chitosan derivatives are carboxymethyl chitosan or N, N- dimethyl chitosan.
Preferably, the anti-aging agent is antioxidant A W and anti-aging agent RD, and the weight ratio of the two is 5:1.
A kind of preparation method for the nitrile rubber composite metal plate that foams, the foaming nitrile rubber composite metal plate includes gold
Belong to substrate, foaming rubber layer is arranged in the surface of the metal substrate, comprising the following steps:
Metal substrate: successively being carried out derusting and ungrease treatment by step S1, removes surface impurity, the metal that obtains that treated
Substrate；
Step S2: adhesive phase is respectively coated in metallic substrate surfaces after the treatment, and described adhesive layer is by thermoplastic
Property phenolic resin, silane coupling agent WD-60, silane coupling A -151 mixed in the ratio of 1:2:1, it is dry after coating, it is spare；
Step S3: nitrile rubber, zinc oxide, carbon black, sulphur, promotor, foaming agent and auxiliary agent are successively put into mixer
It is middle to be kneaded 1 ~ 3 time to obtain rubber compound, after standing 20 ~ 24 hours, stirring 30 minutes or more, it is uniformly mixed, roller coating is in described adhesive
The surface of layer is stood to surface drying；
Step S4: in vulcanizing press carry out composite sulfuration to get.
Preferably, the technological parameter of the vulcanization are as follows: curing temperature is 150 ~ 165 DEG C, and vulcanization time is 18 ~ 35min, sulphur
Change pressure is 8 ~ 12MPa.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of foaming nitrile rubber composite metal plate of excellent combination property through the above technical solution,
The composite plate is by metal substrate and its is coated on the foaming rubber layer of lower surface and forms, and sealing performance is excellent, mechanicalness
Can be good, creep resistant relaxation ability is prominent.
The present invention makes improvements using nitrile rubber as primary raw material, so that its advantage becomes apparent from, defect is obtained effectively
It makes up.Important activity agent of the zinc oxide as rubber materials, be added to improve the heating conduction of product, wear-resisting property and its
Mechanical performance etc. has important influence, it mainly has the function of promoting the vulcanization of rubber and its reinforcement in the present invention, reinforces
Sulfidation shortens vulcanization time, improves the mechanical performance of coating.Although there are many its beneficial effect, dosage is not yet
It is The more the better, improperly meeting is used so that the vulcanization effect of product is insufficient, and coating leveling is bad, causes under sealing performance
Drop.The present invention determines that the additional amount of zinc oxide is 1 ~ 10 parts by weight through repetition test, works well, and is especially 5 weights in additional amount
Effect is optimal when measuring part.On this basis, it is equipped with the promotor of 0.5 ~ 8 parts by weight, preferably is selected from thuriam acceserator or/and secondary
Sulfonamides promotor collectively promotes the abundant progress of nitrile rubber vulcanization reaction, to improve the mechanical performance of product, especially
It is stronger to be resistant to deformability.
For nitrile rubber because belonging to amorphism amorphous polymer, intensity itself is lower, it is necessary to just have after reinforcement
Practical value.Can be used as nitrile rubber reinforcing agent at present has the materials such as carbon black, white carbon black, magnesia, calcium carbonate, different benefits
Strong material and its dosage have different influences to the performance of blown rubber coating.The present invention is determining through repetition test, and opposite 100
For the nitrile rubber of parts by weight, the carbon black of 20 ~ 40 parts by weight of single addition, can very big journey as supporting material of the invention
Degree ground improves the hardness and its adhesive force of blown rubber coating, while flexibility is also more satisfactory, and using 30 parts by weight
Spray carbon black effect be it is best, flow leveling is more preferable, convenient for coating construct.
Nitrile rubber makes its resistance to ag(e)ing, oxidative resistance not as good as other saturated rubbers due to the presence of double bond.In the work of heat
Under, vulcanization crosslinking occurs for sulphur and nitrile rubber, so that so that linear rubber molecule is cross-linked with each other reticulates structure, improves fourth
The stability of nitrile rubber molecular structure enhances the mechanical performance and its chemical property of rubber.The additional amount and its work of sulphur simultaneously
It is also influenced by nitrile rubber foamed state with effect, if foaming blasthole is uniform, suitable sulphur additional amount is enabled to
The state of cure (vulcanization) of blown rubber is more preferable, and product mechanical performance is promoted more significant.And foaming agent is that a kind of heat resolve can generate
The substance of gas, is heated together with nitrile rubber, makes to generate a large amount of bubbles inside rubber using the gas of generation.Aperture
Size and its quantity and type, ratio, the foam process etc. that foaming agent is added have close relationship.The present invention inquired into repeatedly,
It tests and determines that the additional amount of sulphur is 0.5 ~ 5 parts by weight, the usage amount of foaming agent is 1 ~ 5 part, and when foaming agent is azo two
When the composition that formamide and CR-4305 are formed with weight ratio 1:2, resultant effect is optimal.
The compression ratio that the present invention develops foaming nitrile rubber composite metal plate is 32 ~ 47%, rebound degree > 80%, creep pine
Relaxation rate < 4%, leakproofness ml/hr≤0.02, oil seal No leakage, 5 hours weight gain < 2% of the B of resistance to fuel oil room temperature thicken < 4%,
150 DEG C of 5h weight gain < 4% of resistance to ASTM3 oil, thicken < 3%, and composite plate of the present invention shows excellent compression ratio, rebound degree, resists
Croop property and heatproof oil resistance etc..
Specific embodiment
The present invention will be further described with reference to the examples below, but the present invention is not limited to these instances, and is being de-
Under the premise of from present inventive concept, carried out by it is any improvement be within the scope of the present invention.
Embodiment 1
A kind of foaming nitrile rubber composite metal plate, including metal substrate, the surface setting foaming rubber of the metal substrate
Glue-line, the foaming rubber layer are made of the raw material of following mass parts: 100 parts of nitrile rubber, 5 parts of zinc oxide, 4 parts of promotor,
1 part of sulphur, 30 parts of carbon black, 2.2 parts of foaming agent, 4 parts of auxiliary agent.
Wherein, foaming agent is the mixture that azodicarbonamide and CR-4305 are formed with weight ratio 1:2, and auxiliary agent is carboxylic first
The mixture that base enclosure glycan and anti-aging agent are formed with weight ratio 1:1, wherein anti-aging agent is antioxidant A W and anti-aging agent RD, and the two
Weight ratio be 5:1, promotor is raw materials used and its dosage as shown in the table below:
。
In the present invention, metal substrate is selected from carbon steel sheet, stainless steel plate or aluminium alloy plate, is with a thickness of 0.15 ~ 0.2 millimeter
Preferably.
A kind of preparation method for the nitrile rubber composite metal plate that foams of this group of embodiment, the foaming nitrile rubber metal are multiple
Plywood includes metal substrate, and foaming rubber layer is arranged in the surface of the metal substrate, comprising the following steps:
Metal substrate: successively being carried out derusting and ungrease treatment by step S1, removes surface impurity, the metal that obtains that treated
Substrate；Specifically, ungrease treatment is that degreasing agent is diluted with water to 20 times, metal substrate is cleaned, removes surface grease；
Step S2: adhesive phase is respectively coated in metallic substrate surfaces after the treatment, and described adhesive layer is by thermoplastic
Property phenolic resin, silane coupling agent WD-60, silane coupling A -151 mixed in the ratio of 1:2:1, it is dry after coating, it is spare；
Step S3: nitrile rubber, zinc oxide, carbon black, sulphur, promotor, foaming agent and auxiliary agent are successively put into mixer
It is middle to be kneaded 2 times to obtain rubber compound, after standing 24 hours, stirring 30 minutes or more, it is uniformly mixed, table of the roller coating in described adhesive layer
Face is stood to surface drying；
Step S4: composite sulfuration is carried out in vulcanizing press, wherein curing temperature is 150 DEG C, and vulcanization time is
20min, sulfide stress 10MPa.
Embodiment 2
A kind of foaming nitrile rubber composite metal plate, including metal substrate, the surface setting foaming rubber of the metal substrate
Glue-line, the foaming rubber layer are made of the raw material of following mass parts: 100 parts of nitrile rubber, 1 part of zinc oxide, 2 parts of promotor,
0.5 part of sulphur, 20 parts of carbon black, 1 part of foaming agent, 1 part of auxiliary agent.
Wherein, promotor is tetramethylthiuram disulfide and N- cyclohexyl -2-[4-morpholinodithio sulfenamide, the weight of the two
For amount than being 1:1, auxiliary agent is the mixture that carboxymethyl chitosan and anti-aging agent are formed with weight ratio 1:1, and wherein anti-aging agent is anti-old
Agent AW and anti-aging agent RD, and the weight ratio of the two is 5:1, foaming agent is raw materials used and its dosage is as shown in the table:
。
A kind of preparation method for the nitrile rubber composite metal plate that foams of this group of embodiment, the foaming nitrile rubber metal are multiple
Plywood includes metal substrate, and foaming rubber layer is arranged in the surface of the metal substrate, comprising the following steps:
Metal substrate: successively being carried out derusting and ungrease treatment by step S1, removes surface impurity, the metal that obtains that treated
Substrate；Specifically, ungrease treatment is that degreasing agent is diluted with water to 20 times, metal substrate is cleaned, removes surface grease；
Step S2: adhesive phase is respectively coated in metallic substrate surfaces after the treatment, and described adhesive layer is by thermoplastic
Property phenolic resin, silane coupling agent WD-60, silane coupling A -151 mixed in the ratio of 1:2:1, it is dry after coating, it is spare；
Step S3: nitrile rubber, zinc oxide, carbon black, sulphur, promotor, foaming agent and auxiliary agent are successively put into mixer
It is middle to be kneaded 3 times to obtain rubber compound, after standing 20 hours, stirring 30 minutes or more, it is uniformly mixed, table of the roller coating in described adhesive layer
Face is stood to surface drying；
Step S4: composite sulfuration is carried out in vulcanizing press, wherein curing temperature is 160 DEG C, and vulcanization time is
18min, sulfide stress 12MPa.
Embodiment 3
A kind of foaming nitrile rubber composite metal plate, including metal substrate, the surface setting foaming rubber of the metal substrate
Glue-line, the foaming rubber layer are made of the raw material of following mass parts: 100 parts of nitrile rubber, 10 parts of zinc oxide, promotor 10
Part, 5 parts of sulphur, 40 parts of carbon black, 5 parts of foaming agent, 10 parts of auxiliary agent.
Wherein, foaming agent is the mixture that azodicarbonamide and CR-4305 are formed with weight ratio 1:2, promotor two
Vulcanize tetra methylthiuram and N- cyclohexyl -2-[4-morpholinodithio sulfenamide, the weight ratio of the two is 1:1, and auxiliary agent is raw materials used
And its dosage is as follows:
。
A kind of preparation method for the nitrile rubber composite metal plate that foams of this group of embodiment, the foaming nitrile rubber metal are multiple
Plywood includes metal substrate, and foaming rubber layer is arranged in the surface of the metal substrate, comprising the following steps:
Metal substrate: successively being carried out derusting and ungrease treatment by step S1, removes surface impurity, the metal that obtains that treated
Substrate；Specifically, ungrease treatment is that degreasing agent is diluted with water to 20 times, metal substrate is cleaned, removes surface grease；
Step S2: adhesive phase is respectively coated in metallic substrate surfaces after the treatment, and described adhesive layer is by thermoplastic
Property phenolic resin, silane coupling agent WD-60, silane coupling A -151 mixed in the ratio of 1:2:1, it is dry after coating, it is spare；
Step S3: nitrile rubber, zinc oxide, carbon black, sulphur, promotor, foaming agent and auxiliary agent are successively put into mixer
It is middle to be kneaded 2 times to obtain rubber compound, after standing 24 hours, stirring 30 minutes or more, it is uniformly mixed, table of the roller coating in described adhesive layer
Face is stood to surface drying；
Step S4: composite sulfuration is carried out in vulcanizing press, wherein curing temperature is 165 DEG C, and vulcanization time is
35min, sulfide stress 8MPa.
Embodiment 4
A kind of foaming nitrile rubber composite metal plate, including metal substrate, the surface setting foaming rubber of the metal substrate
Glue-line, the foaming rubber layer are made of the raw material of following mass parts: 100 parts of nitrile rubber, 3 parts of zinc oxide, 6 parts of promotor,
2.5 parts of sulphur, 25 parts of carbon black, 1.5 parts of foaming agent, 3 parts of auxiliary agent.
Wherein, foaming agent is the mixture that azodicarbonamide and CR-4305 are formed with weight ratio 1:2, and auxiliary agent is 1.5 weights
The N of part, the anti-aging agent RD of N- dimethyl chitosan and 1.5 parts by weight are measured, promotor is tetramethylthiuram disulfide and N- ring
Base -2-[4-morpholinodithio sulfenamide, the weight ratio of the two are 1:1.
Embodiment 5
A kind of foaming nitrile rubber composite metal plate, including metal substrate, the surface setting foaming rubber of the metal substrate
Glue-line, the foaming rubber layer are made of the raw material of following mass parts: 100 parts of nitrile rubber, 8 parts of zinc oxide, 7 parts of promotor,
4 parts of sulphur, 35 parts of carbon black, 4 parts of foaming agent, 8 parts of auxiliary agent.
Wherein, foaming agent CR-4305, auxiliary agent are antioxidant A W, and promotor is tetramethylthiuram disulfide and N- ring
Base -2-[4-morpholinodithio sulfenamide, the weight ratio of the two are 1:1.
Effect assessment
To the foaming nitrile rubber composite metal plate developed of the present invention carry out compression recovery performance, creep relaxation performance,
Medium-resistance, sealing performance etc. are tested, and test result average value is listed in the table below:
Connect table:
To sum up, the present invention develops foam nitrile rubber composite metal plate compression ratio be 32 ~ 47%, rebound degree > 80%,
Creep relaxation rate < 4%, leakproofness ml/hr≤0.02, oil seal No leakage, 5 hours weight gain < 2% of the B of resistance to fuel oil room temperature are thickened
< 4%, 150 DEG C of 5h of resistance to ASTM3 oil increase weight < 4%, thicken < 3%, in a word composite plate show excellent compression ratio, rebound degree,
Creep-resistant property and heatproof oil resistance etc., resultant effect is very prominent.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, this field is common
Other modifications or equivalent replacement that technical staff makes technical solution of the present invention, without departing from technical solution of the present invention
Spirit and scope, be intended to be within the scope of the claims of the invention.
Claims (3)
1. a kind of foaming nitrile rubber composite metal plate, it is characterised in that: including metal substrate, the surface of the metal substrate is set
Set foaming rubber layer, the foaming rubber layer is made of the raw material of following mass parts: 100 parts of nitrile rubber, 1~3 part of zinc oxide,
10 parts of promotor, 0.5~5 part of sulphur, 20~35 parts of carbon black, 1~5 part of foaming agent, 3~10 parts of auxiliary agent,
The foaming agent is azodicarbonamide and CR-4305, and the weight ratio of the azodicarbonamide and CR-4305 are 1:2
~3,
The promotor is tetramethylthiuram disulfide and N- cyclohexyl -2-[4-morpholinodithio sulfenamide, the weight ratio of the two
For 0.8~1:1,
The auxiliary agent be chitosan derivatives and anti-aging agent,
The chitosan derivatives be carboxymethyl chitosan or N, N- dimethyl chitosan,
The anti-aging agent is antioxidant A W and anti-aging agent RD, and the weight ratio of the two is 5:1.
2. the preparation method of foaming nitrile rubber composite metal plate as described in claim 1, it is characterised in that: the foaming fourth
Nitrile rubber composite metal plate includes metal substrate, and foaming rubber layer is arranged in the surface of the metal substrate, comprising the following steps:
Metal substrate: successively being carried out derusting and ungrease treatment by step S1, removes surface impurity, the Metal Substrate that obtains that treated
Plate；
Step S2: adhesive phase is respectively coated in metallic substrate surfaces after the treatment, and described adhesive layer is by thermoplasticity phenol
Urea formaldehyde, silane coupling agent WD-60, silane coupling A -151 are mixed in the ratio of 1:2:1, dry after coating, spare；
Step S3: nitrile rubber, zinc oxide, carbon black, sulphur, promotor, foaming agent and auxiliary agent are successively put into mixer and mixed
Rubber compound is refined 1~3 time to obtain, after standing 20~24 hours, stirring 30 minutes or more, is uniformly mixed, roller coating is in described adhesive layer
Surface, stand to surface drying；
Step S4: in vulcanizing press carry out composite sulfuration to get.
3. a kind of preparation method of nitrile rubber composite metal plate that foams as claimed in claim 2, it is characterised in that: the sulphur
The technological parameter of change are as follows: curing temperature is 150~165 DEG C, and vulcanization time is 18~35min, and sulfide stress is 8~12MPa.
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| CN109206686A (en) * | 2018-07-14 | 2019-01-15 | 桂林理工大学 | A kind of nitrile rubber-metal composite sealing material and preparation method thereof |
| CN109535853A (en) * | 2018-10-29 | 2019-03-29 | 胡果青 | A kind of preparation method of blown rubber composite metal plate |
| CN109703035B (en) * | 2018-12-27 | 2021-06-15 | 南阳天一密封股份有限公司 | Preparation method of anti-attenuation gasket |
| CN112375269A (en) * | 2020-10-16 | 2021-02-19 | 江门市新会区天府密封科技有限公司 | Rubber foamed sealing material |
| CN113527951B (en) * | 2021-07-05 | 2022-09-20 | 西安理工大学 | Absorption protective layer and coating method for surface of metal part |
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| CN115156014B (en) * | 2022-07-28 | 2023-09-19 | 宁波信幸隆密封制品有限公司 | Processing technology of rubber metal local foaming composite gasket |
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