CN102108274B - Phenolic-nitrile rubber hot vulcanized adhesive and preparation method thereof - Google Patents
Phenolic-nitrile rubber hot vulcanized adhesive and preparation method thereof Download PDFInfo
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- CN102108274B CN102108274B CN 201110029305 CN201110029305A CN102108274B CN 102108274 B CN102108274 B CN 102108274B CN 201110029305 CN201110029305 CN 201110029305 CN 201110029305 A CN201110029305 A CN 201110029305A CN 102108274 B CN102108274 B CN 102108274B
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- phenolic
- nitrile rubber
- vulcanized adhesive
- hot vulcanized
- rubber hot
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- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 47
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920001971 elastomer Polymers 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 5
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- 230000008961 swelling Effects 0.000 claims abstract description 4
- 229920003987 resole Polymers 0.000 claims description 20
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 12
- 244000226021 Anacardium occidentale Species 0.000 claims description 9
- 235000020226 cashew nut Nutrition 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 239000012764 mineral filler Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- WYRGOSDNPFGZFG-UHFFFAOYSA-K [bis(2-ethylhexoxy)-oxidophosphaniumyl] dihydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] hydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] phosphate propan-2-olate titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)(O)=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)([O-])=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP([O-])([O-])=O WYRGOSDNPFGZFG-UHFFFAOYSA-K 0.000 claims description 3
- -1 alkyl phenolic resin Chemical compound 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 abstract 2
- 239000011256 inorganic filler Substances 0.000 abstract 2
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 2
- 239000002002 slurry Substances 0.000 abstract 2
- 238000010008 shearing Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000005987 sulfurization reaction Methods 0.000 description 6
- 238000004513 sizing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 150000008363 butyronitriles Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920013649 Paracril Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100116805 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SDH4 gene Proteins 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000595 mu-metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
The invention discloses a phenolic-nitrile rubber hot vulcanized adhesive and a preparation method thereof. The adhesive consists of the following raw materials: crude nitrile rubber, phenolic resin, an inorganic filler, a vulcanizing agent, a tackifying resin, a coupling agent, an anti-aging agent and methyl isobutyl ketone. The preparation method comprises the following steps of: plasticating the crude nitrile rubber for 1 to 3 minutes on an open mill; sequentially adding the tackifying resin, the inorganic filler, the coupling agent, the anti-aging agent and the vulcanizing agent into the open mill for mixing; after plasticating the mixture, shearing the mixture; adding the sheared mixture into the methyl isobutyl ketone for swelling; after stirring and dissolving the mixture, obtaining a rubber slurry; and adding the phenolic resin into the rubber slurry to obtain the phenolic-nitrile rubber hot vulcanized adhesive after uniformly stirring the mixture.
Description
One, technical field
The present invention relates to a kind of sizing agent and preparation method thereof, specifically a kind of phenolic-nitrile rubber hot vulcanized adhesive and preparation method thereof.
Two, background technology
In the metal construction sizing agent, phenolic-nitrile rubber hot vulcanized adhesive be current synthetic adhesive performance comprehensively, purposes sizing agent more widely.Since nineteen forty-three, the U.S. delivered first phenolic-nitrile rubber hot vulcanized adhesive Metlbond4021, its history was still used in aircraft manufacturing for 60 years so far in a large number.Why phenolic-nitrile rubber hot vulcanized adhesive can keep this status, except it is cheap, relevant with its following characteristics:
1, the various metallic substance of bonding have higher physical and mechanical properties in relatively broader temperature range;
2, have preferably elasticity and toughness, thereby have higher stripping strength, resistance to impact shock and fatigue property;
3, have good resistant to thermal aging, deterioration with moisture and atmospheric aging performance;
4, have the dielectric behaviors such as good anti-lubricating oil, fuel oil, self solvent, second alcohol and water, and good salt spray resistance;
5, have excellent fatigue property and enduring quality;
6, processing performance is good, and is easy to use;
7, applied range, bonding except applied metal also is used for bonding brake facing band and clutch disc, and for example domestic J-04 glue has obtained good effect applying of bonding brake facing band.
Phenolic-nitrile rubber hot vulcanized adhesive can be used for the hot sulfurization bonding of butadiene-acrylonitrile rubber and hydrogenated butyronitrile glue and the metallic framework of different acrylonitrile contents.The tackiness agent that can reach in the market this requirement is primer chemlock205, the face glue chemlock6125 that U.S. Kai Muluoke company provides.The used solvent of its primer is hexone, and little poison has a little smell; The used solvent of face glue is dimethylbenzene, and toxicity is large, and the smell is awful.Employed is spraying coating process, and the utilization ratio of sizing agent is low.Price is relatively expensive at present.
Three, summary of the invention
The present invention aims to provide a kind of excellent property, cheap phenolic-nitrile rubber hot vulcanized adhesive and preparation method thereof.The technical issues that need to address are to reduce its cost and toxicity under the prerequisite that guarantees hot sulfurization gluing agent performance.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention are that its raw material constitutes by mass percentage:
Butyronitrile rubber 7-10%
Resol 8-15%
Mineral filler 0.5-1%
Vulcanizing agent 0.5-1%
Tackifying resin 1-2%
Coupling agent 1-2.5%
Anti-aging agent 0.1-0.5%
The hexone surplus.
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention also are: described resol is the resol of cashew nut modification.
Contain methylol and dimethylene ehter bond in the resol of one of the bonding material of selecting cashew nut modification, and must consider that the curing speed of resol itself and the speed of response of resol and paracril coordinate mutually during the resol of selecting.Methylol and dimethylene ehter bond can generate inner complex with reactive metal oxide, can form the extensive chemical bonding action with the metallic surface; Methylol also can with rubber molecule in two keys form the oxa-naphthalene structures, rubber is had special sulfuration promoter action.Therefore, bonding strength is higher.
Dibutyronitrile rubber and the metal of the bonding material of selecting have good wettability and adsorption, have high tack; And with had good compatiblely by sticking rubber, can drive and work in coordination with other components and in Vulcanization Process of Rubber, form stable transition layer.
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention also are: described mineral filler is selected from one or more mixed fillers in titanium dioxide, light calcium carbonate, white carbon black, the potter's clay, can improve cohesive strength and the thermotolerance of tackiness agent.
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention also are: described vulcanizing agent is selected from one or more mixing vulcanizing agent in Sulfur, sulfocompound, organo-peroxide, the metal oxide, participates in the covulcanization of rubber.
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention also are: described tackifying resin is selected from one or more hybrid resin in petroleum resin, Gum Rosin, the alkyl phenolic resin, and purpose is to increase adhesion.
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention also are: described coupling agent is selected from one or more mixing coupling agent in silane coupling agent, the titanate coupling agent.
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention also are: described silane coupling agent is selected from KH-550, KH-560, KH-570 or KH-590; Described titanate coupling agent is selected from NDZ-102, NDZ-105, NDZ-130 or NDZ-201.
Coupling agent is the compound that the difference in functionality group is contained at the molecule two ends, the one end can with the inorganic material surface bonding, the other end then can react with organic materials, builds bridge between two kinds of differing materials with the form of chemical bond, and they are combined securely.Add coupling agent in the tackiness agent, it both can form bridge formation between by sticking metallic surface and adhesive linkage, can build bridge at adhesive linkage and by sticking rubber surface again, and can improve the cohesive strength of adhesive linkage.Test-results shows that when adding 1～2.5% coupling agent, 90 ° of stripping strengths are 8.7kN/m, and collapse mode is the rubber cohesive failure; And the person that do not add the coupling agent, stripping strength 5.8kN/m, the effect of coupling agent is obvious.
The characteristics of phenolic-nitrile rubber hot vulcanized adhesive of the present invention also are: described anti-aging agent is selected from one or more blended antioxidant in Resorcinol, 2,6 ditertiary butyl p cresol, the hydroquinone dimethyl ether.Anti-aging agent can not be selected some Ammonia anti-aging agent such as 4010NA, 4110 and antioxidant D etc., because they can cause the condensation cured of resol self.
The solvent of selecting is single hexone, and it has good solvency action to resol and paracril.And hexone solvent low toxicity and good to the resol solubility property, its oil soluble characteristic makes filler obtain Uniform Dispersion.
The preparation method's of phenolic-nitrile rubber hot vulcanized adhesive of the present invention characteristics are to operate according to the following steps: the butyronitrile rubber was plasticated 1-3 minute in mill, then tackifying resin, mineral filler, coupling agent, anti-aging agent and vulcanizing agent are added successively carry out mixing, shred after the thin-pass and drop into immediately swelling in the hexone, get rubber cement after the stirring and dissolving, in described rubber cement, add resol, namely get phenolic-nitrile rubber hot vulcanized adhesive after stirring.
The physical and chemical performance of the tackiness agent of the present invention's preparation is as follows:
| Outward appearance | Yellow viscous liquid |
| Solids content/% | 20-26 |
| The pH value | 7.0-7.6 |
| Viscosity/cP, 20 ℃ | 220-500 |
| Free formaldehyde/% | ≯1.5 |
| Preservation period/d | 30-60 |
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the used solvent hexone of sizing agent of the present invention is the 3rd kind solvent to the human body low toxicity;
2, the used cost value of the present invention is cheap;
What adopt when 3, the present invention uses is gum dipping process, and the skeleton pre-treatment is simple, convenient.
Four, embodiment:
The butyronitrile rubber that uses in following examples is butyronitrile-41 rubber, and mooney viscosity is at 70-80, trade mark N21, and petro-chemical corporation provides by Lanzhou of China; The resol of cashew nut modification, trade mark FBS, high-temperature resin Materials Co., Ltd provides by the sky, Bangbu.
Embodiment 1:
The raw material of phenolic-nitrile rubber hot vulcanized adhesive constitutes by mass percentage in the present embodiment: butyronitrile rubber 7%, the resol 8% of cashew nut modification, titanium dioxide 0.5%, Sulfur 0.5%, petroleum resin 1%, KH-5501%, Resorcinol 0.1%, the hexone surplus.
The preparation method of phenolic-nitrile rubber hot vulcanized adhesive operates according to the following steps in the present embodiment:
The butyronitrile rubber was plasticated 1-3 minute in mill, make its mooney viscosity reach 60～70, then tackifying resin, mineral filler, coupling agent, anti-aging agent and vulcanizing agent are added successively carry out mixing, distance between mill two rollers is 1-2mm, shred after the thin-pass and drop into immediately swelling in the hexone, after the stirring and dissolving rubber cement, add the resol of cashew nut modification in the described rubber cement, namely get phenolic-nitrile rubber hot vulcanized adhesive after stirring.
Embodiment 2:
The raw material of phenolic-nitrile rubber hot vulcanized adhesive constitutes by mass percentage in the present embodiment: butyronitrile rubber 10%, the resol 15% of cashew nut modification, light calcium carbonate 1%, dibenzothiazyl disulfide 1%, Gum Rosin 2%, KH-570 2.5%, 2,6-ditertbutylparacresol 0.5%, the hexone surplus.
The preparation method of phenolic-nitrile rubber hot vulcanized adhesive is with embodiment 1 in the present embodiment.
Embodiment 3:
The raw material of phenolic-nitrile rubber hot vulcanized adhesive constitutes by mass percentage in the present embodiment: butyronitrile rubber 8%, the resol 10% of cashew nut modification, white carbon black and titanium dioxide 0.7%, dicumyl peroxide 0.6%, alkyl phenolic resin 1.5%, NDZ-102 1.5%, hydroquinone dimethyl ether 0.3%, hexone surplus.
The preparation method of phenolic-nitrile rubber hot vulcanized adhesive is with embodiment 1 in the present embodiment.
Embodiment 4:
The raw material of phenolic-nitrile rubber hot vulcanized adhesive constitutes by mass percentage in the present embodiment: butyronitrile rubber 9%, the resol 12% of cashew nut modification, potter's clay 0.8%, zinc oxide 0.8%, Gum Rosin 2%, NDZ-201 2%, Resorcinol 0.4%, the hexone surplus.
The preparation method of phenolic-nitrile rubber hot vulcanized adhesive is with embodiment 1 in the present embodiment.
The phenolic-nitrile rubber hot vulcanized adhesive of the present invention preparation is used for the butadiene-acrylonitrile rubber of different acrylonitrile contents and hydrogenated butyronitrile glue to carry out hot sulfurization with the phosphatization skeleton and bonds, and coheres 90 ° of stripping tests (title stripping strength) by GB/T 7760-2003 vulcanized rubber and metal and detects:
1, place: Anhui Ningguo sealing member limited-liability company, sealing member workshop;
2, the object of adhesive test: bonding between the butyronitrile rubber unvulcanizate of different acrylonitrile contents (N736 (ACN41%), N7299 (ACN33%), N708 (ACN29%), N7159 (ACN26%), N7326 (ACN18%)) and hydrogenated butyronitrile rubber unvulcanizate M708KL and the parkerized metallic framework (carbon steel material);
3, test operation process:
(1) glue dilution: dilute phenolic-nitrile rubber hot vulcanized adhesive with butanone, the quality of butanone is the twice of phenolic-nitrile rubber hot vulcanized adhesive quality.
(2) coating technique: adopt the dipping method, parkerized metallic framework is dipped in the tackiness agent after the dilution;
(3) Procuring is processed: the phosphating metal skeleton behind the impregnation carries out Procuring, the Procuring condition: solidify 10min in 170 ℃ behind the impregnation for the first time; Solidify 10min in 100 ℃ behind the impregnation for the second time;
(4) sulfuration: the phosphating metal skeleton after Procuring is processed pastes rubber unvulcanizate not of the same race and carries out bonding by Vulcanization, cure conditions: pressure 15MPa, 175 ℃ of temperature, time 240s.
4, test evaluation method: destroy type according to sample and judge: R-rubber destroys; RC-rubber and polymer adhesive interface layer destroy; CP-polymer adhesive layer and primer interface layer destroy (as using primer); The interface is destroyed between CM-adhesive linkage and metal base; The sample of D-adhesive-free directly occurs in the interfacial failure between rubber and metal base; The M-metal base destroys; That the R type is the Pass Test requirement such as 100%.
*The butyronitrile rubber unvulcanizate of the different trades mark of N736-N220～N7326L-N250; The M708KL-hydrogenated butyronitrile rubber unvulcanizate trade mark.
*The english abbreviation of AN-acrylonitrile monemer.
*The hot sulfurization gluing agent Korea S TD870 that uses for butyronitrile oil sealing general on the present market: only the 90 ° of stripping strengths of bonding for metal and N713K-N230 (AN content 33%) are 5.98kN/m, and it is that the whole rubber of R-destroy that sample destroys type.
Claims (8)
1. phenolic-nitrile rubber hot vulcanized adhesive is characterized in that its raw material constitutes by mass percentage:
Described resol is the resol of cashew nut modification.
2. phenolic-nitrile rubber hot vulcanized adhesive according to claim 1, it is characterized in that: described mineral filler is selected from one or more mixed fillers in titanium dioxide, light calcium carbonate, white carbon black, the potter's clay.
3. phenolic-nitrile rubber hot vulcanized adhesive according to claim 1 is characterized in that: described vulcanizing agent is selected from Sulfur, sulfocompound, organo-peroxide, the metal oxide one or more and mixes vulcanizing agent.
4. phenolic-nitrile rubber hot vulcanized adhesive according to claim 1, it is characterized in that: described tackifying resin is selected from one or more hybrid resin in petroleum resin, Gum Rosin, the alkyl phenolic resin.
5. phenolic-nitrile rubber hot vulcanized adhesive according to claim 1 is characterized in that: described coupling agent is selected from silane coupling agent, the titanate coupling agent one or more and mixes coupling agent.
6. phenolic-nitrile rubber hot vulcanized adhesive according to claim 5, it is characterized in that: described silane coupling agent is selected from KH-550, KH-560, KH-570 or KH-590; Described titanate coupling agent is selected from NDZ-102, NDZ-105, NDZ-130 or NDZ-201.
7. phenolic-nitrile rubber hot vulcanized adhesive according to claim 1, it is characterized in that: described anti-aging agent is selected from one or more blended antioxidant in Resorcinol, 2,6 ditertiary butyl p cresol, the hydroquinone dimethyl ether.
8. the preparation method of phenolic-nitrile rubber hot vulcanized adhesive according to claim 1, it is characterized in that operating according to the following steps: the butyronitrile rubber was plasticated 1-3 minute in mill, then tackifying resin, mineral filler, coupling agent, anti-aging agent and vulcanizing agent are added successively carry out mixing, shred after the thin-pass and drop into immediately swelling in the hexone, get rubber cement after the stirring and dissolving, in described rubber cement, add resol, namely get phenolic-nitrile rubber hot vulcanized adhesive after stirring.
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| CN 201110029305 CN102108274B (en) | 2011-01-27 | 2011-01-27 | Phenolic-nitrile rubber hot vulcanized adhesive and preparation method thereof |
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| CN 201110029305 CN102108274B (en) | 2011-01-27 | 2011-01-27 | Phenolic-nitrile rubber hot vulcanized adhesive and preparation method thereof |
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| CN102108274B true CN102108274B (en) | 2013-03-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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