CN115141579A - High-durability flexible rubber metal adhesive surface coating agent and application thereof - Google Patents
High-durability flexible rubber metal adhesive surface coating agent and application thereof Download PDFInfo
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- CN115141579A CN115141579A CN202110925069.5A CN202110925069A CN115141579A CN 115141579 A CN115141579 A CN 115141579A CN 202110925069 A CN202110925069 A CN 202110925069A CN 115141579 A CN115141579 A CN 115141579A
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- rubber
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- containing compound
- metal adhesive
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 153
- 239000000853 adhesive Substances 0.000 title claims abstract description 45
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 35
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000002955 isolation Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920000459 Nitrile rubber Polymers 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 claims description 9
- 229920005556 chlorobutyl Polymers 0.000 claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- XYLFFOSVQCBSDT-UHFFFAOYSA-N 1,2-dinitrosobenzene Chemical compound O=NC1=CC=CC=C1N=O XYLFFOSVQCBSDT-UHFFFAOYSA-N 0.000 claims description 2
- JLNGXFCCWYKFIX-UHFFFAOYSA-N 1,3-dinitrosobenzene Chemical compound O=NC1=CC=CC(N=O)=C1 JLNGXFCCWYKFIX-UHFFFAOYSA-N 0.000 claims description 2
- MKZXROSCOHNKDX-UHFFFAOYSA-N 1,4-dinitrosobenzene Chemical compound O=NC1=CC=C(N=O)C=C1 MKZXROSCOHNKDX-UHFFFAOYSA-N 0.000 claims description 2
- NYJYFSGMYHSTNZ-UHFFFAOYSA-N 1-methyl-4-nitrosobenzene Chemical compound CC1=CC=C(N=O)C=C1 NYJYFSGMYHSTNZ-UHFFFAOYSA-N 0.000 claims description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920005557 bromobutyl Polymers 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920002681 hypalon Polymers 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 19
- 238000009413 insulation Methods 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 229920001967 Metal rubber Polymers 0.000 abstract description 2
- 238000013016 damping Methods 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- 239000008096 xylene Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000006757 chemical reactions by type Methods 0.000 description 7
- 230000006378 damage Effects 0.000 description 7
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical class ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- AELWIPRGNLGYSD-UHFFFAOYSA-N ethyl acetate;1-methoxypropan-2-ol Chemical compound CCOC(C)=O.COCC(C)O AELWIPRGNLGYSD-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 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
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005728 strengthening Methods 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J115/00—Adhesives based on rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Abstract
The invention relates to the technical field of damping metal-rubber bonding, in particular to a high-durability flexible rubber metal bonding surface coating agent and application thereof. The raw materials comprise the following components in percentage by mass: 5-30% of film-forming agent, 5-15% of functional rubber, 5-20% of modified rubber, 1-15% of filler and the balance of solvent; the modified rubber is a reactive rubber modified with a nitrogen-containing compound. When the flexible rubber metal adhesive surface coating agent with high durability is used for bonding a seismic isolation support, the ultimate deformation resistance is obviously superior to that of the traditional adhesive combination. The invention can effectively increase the strength and flexibility of the bonding interface, so that the shock insulation support has better shock absorption performance when being deformed by stress, and the durability of the product is greatly improved.
Description
Technical Field
The invention relates to the technical field of damping metal-rubber bonding, in particular to a high-durability flexible rubber metal bonding surface coating agent and application thereof.
Background
At present, rubber and metal bonding products are widely applied to seismic isolation and sealing, not only the rigidity of metal is kept, but also the elasticity of rubber is considered, and the application scenes are perfectly matched. The rubber metal adhesive is a name of industrial monosodium glutamate in the industries of automobile parts, plate type supports, shock insulation supports, rubber tracks, wharf fenders and the like.
The shock insulation support is a support device arranged for meeting the shock insulation requirement of a structure, a shock insulation layer is additionally arranged between an upper structure and a foundation, a rubber shock insulation support is installed to achieve soft connection with the ground, and through the technology, about 80% of energy of an earthquake can be offset. Such as laminated rubber mounts (or seismic isolation rubber mounts, laminated rubber pads, etc.). The structural member has small horizontal rigidity and large vertical rigidity, can bear large horizontal deformation, and can be used as a part of a load-bearing system. Because the civil building has low maintenance frequency and high replacement difficulty, the corresponding requirement on the durability of the support is higher, and the service life of the support is theoretically the same as that of the building, so that the requirement on the adhesive is also provided. The traditional adhesive used for adhering rubber and metal on the vibration isolation support has weaker deformation capacity under the limit shearing action force, and the fracture of an adhesive layer often occurs under the shearing force generated during vibration, so that the vibration isolation support loses the effects of vibration isolation and vibration absorption.
Disclosure of Invention
Aiming at the technical problems, the invention provides a high-durability flexible rubber metal adhesive surface coating agent, which has the functions of strengthening crosslinking and toughening in a system by adopting specific modified rubber, so that a final adhesive finished product has better flexibility and better durability, and a seismic isolation support manufactured by bonding the adhesive finished product by the adhesive has longer service life.
Specifically, the invention provides a high-durability flexible rubber-metal adhesive surface coating agent, which comprises the following raw materials in percentage by mass:
the modified rubber is a reactive rubber modified with a nitrogen-containing compound.
Further, the raw materials of the high-durability flexible rubber metal adhesive surface coating agent comprise the following components in percentage by mass:
the modified rubber is a reactive rubber modified with a nitrogen-containing compound.
As a preferable technical scheme, the raw materials of the nitrogen-containing compound modified reaction type rubber comprise a nitrogen-containing compound and a rubber base material; preferably, the modified rubber component is prepared by reacting a rubber base material with a nitrogen-containing compound in a liquid phase.
Further, the nitrogen-containing compound includes, but is not limited to, one or more of nitrobenzene, nitrosobenzene, p-nitrotoluene, p-nitrosotoluene, p-dinitrosobenzene, m-dinitrosobenzene, o-dinitrosobenzene, and p-benzoquinone dioxime.
Further preferably, the nitrogen-containing compound is a compound containing an oxime group; further, the nitrogen-containing compound is p-benzoquinone dioxime (CAS: 105-11-3).
As a preferable technical scheme, the rubber base material is a hydroxyl-terminated rubber material and/or an epoxy-terminated rubber material.
Further, the hydroxyl-terminated rubber material and the epoxy-terminated rubber material are selected from one or more of hydroxyl-terminated nitrile rubber, epoxy-terminated nitrile rubber, hydroxyl-terminated butyl rubber, epoxy-terminated butyl rubber, hydroxyl-terminated chloroprene rubber and epoxy-terminated chloroprene rubber.
Further, the mass content of the nitrogen-containing compound accounts for at least 20% of the sum of the mass of the nitrogen-containing compound and the mass of the rubber base material.
Further, the mass content of the nitrogen-containing compound accounts for at least 25% of the total mass of the nitrogen-containing compound and the rubber base material.
Preferably, the mass content of the nitrogen-containing compound is not more than 40% of the sum of the mass of the nitrogen-containing compound and the mass of the rubber base material. Further, the mass ratio of the nitrogen-containing compound to the rubber base material may be 8.
More preferably, the mass content of the nitrogen-containing compound is 25 to 35% of the total mass of the nitrogen-containing compound and the rubber base material.
As a preferable technical scheme, the preparation method of the modified rubber comprises the following steps:
adding a rubber base material into a benzene solvent, stirring and dissolving to obtain a rubber solution with the solid content of 30-40 w%, adding the rubber solution into a reaction kettle, replacing air in the reaction kettle with nitrogen, adding the nitrogen-containing compound, reacting for 4-8 hours at 55-70 ℃, heating to 75-85 ℃, treating for 20-45 min, cooling to room temperature, and filtering to obtain the rubber-modified polypropylene composite material.
In the present invention, the benzene solvent may include, but is not limited to, toluene, xylene, etc.
Further, the content of the modified rubber at least accounts for 10wt% of the high-durability flexible rubber-metal adhesive surface coating material; further, it is at least 12wt%; further, it is contained in an amount of at most 20wt%; further, the content thereof is at most 18wt%.
The applicant finds that under the application scene of the shock insulation support, the limit shear deformation of the shock insulation support made of the traditional adhesive product on the market is generally 400-450%, and because the bonding strength between the surface coating agent and the rubber base material is weaker than the strength of the rubber base material, or the strength of the bonding interface is weaker than the strength of the rubber body, when the limit shear deformation test is carried out, most of the damage surface is on the bonding interface of the surface coating adhesive and the rubber, so that the application of the shock insulation support is limited to a certain extent. In the process of completing the invention, the applicant finds that the improved rubber obtained by improving the surface coating agent by adopting a proper amount of the nitrogen-containing compound can obviously improve the deformation result of the surface coating agent under the action of extreme shear, so that the surface coating agent can generate larger deformation, and the effects of shock absorption and shock insulation can be still maintained under stronger acting force. Meanwhile, when the rubber material is damaged, the interface between the rubber and the surface coating agent is kept intact, and the rubber material is torn and damaged. The applicant speculates that the addition of the specific reaction type modified rubber component leads the surface coating agent to penetrate into the rubber substrate and react with related groups in the rubber substrate under the action of additional components such as a primer and the like when bonding metal and the rubber substrate, or react with other structures in the surface coating agent after penetrating into the rubber substrate to form a dense cross-linked network to coat the surface of the rubber substrate, so that the bonding strength can be further improved on the premise that the bonding surface is more flexible, the strength of the bonding interface is greater than the strength of the rubber body, and the maximum limit deformation of 'no damage to rubber and no damage' is realized in the using process.
However, the applicant has found that the content of the nitrogen-containing compound in the modified rubber cannot be too high, and that the amount of the modified rubber in the raw material of the topcoat agent is appropriate, otherwise the deformation rate of the topcoat agent when the extreme shear test is performed is significantly affected. Specifically, the applicant found that when the content of the nitrogen-containing compound used in the modified rubber component is less than 20% by weight (percentage of the total mass of the nitrogen-containing compound and the rubber base material), the effect on the ultimate shear deformation of the topcoat agent is insignificant, and when the content thereof exceeds 40%, the ultimate shear deformation of the topcoat agent starts to decrease, and although the tearing of the rubber base material portion and the integrity of the bonded surface can still be maintained, the ultimate shear deformation thereof is far less than that in the range of 25 to 35% as a result of the content of the nitrogen-containing compound. Further, on the premise that the content of the nitrogen-containing compound in the above-mentioned modified rubber is determined, it is not necessary that the higher the content of the modified rubber is, the better the performance of the topcoat agent is. The Applicant has found that the ultimate shear deformation of the topcoat is reduced to a certain extent when the modified rubber content is greater than 20%, while, likewise, the ultimate shear deformation of the topcoat is likewise improved to a lesser extent when the modified rubber content is less than 12%, in particular less than 10%, the result being far from the case where the modified rubber content is in the range from 12 to 18% by weight, in particular when a film former is used, which is a chlorinated butyl rubber having a chlorine content of 1.26. + -. 0.08 and a Mooney viscosity of 38. + -.5, and the functional rubber is a polyvinyl butyral having a vinyl butyral content of 68 to 80%. The applicant speculates that when the amount of the nitrogen-containing compound in the improved rubber is too high, or the content of the improved rubber in the topcoat agent is too high, the crosslinking density during the bonding of the topcoat agent and the rubber substrate may be too high, and even the rubber layer in the bonding interface may become brittle, so that the deformation amount thereof does not increase or decrease.
As a preferable technical scheme, the functional rubber is selected from one or more of chlorosulfonated polyethylene, chlorosulfonated polypropylene, polyisoprene, polyvinyl butyral and polyvinyl alcohol.
As a preferable technical scheme, the film forming agent is selected from one or more of chlorinated natural rubber, highly chlorinated chloroprene rubber, chlorinated polyethylene, chlorinated polypropylene, chlorinated butyl rubber and brominated butyl rubber.
As a preferred technical scheme, the filler is carbon black.
Further preferably, the carbon black includes, but is not limited to, carbon black with the trade names of N220, N326, N330, N550, N660, N762 and N774.
The solvent component of the high-durability flexible rubber-metal adhesive surface coating agent is not particularly limited in the present invention, and various solvents known to those skilled in the art can be selected, including but not limited to benzene solvents, ester solvents, ketone solvents, etc.
Further, the solvent is selected from one or more of xylene, toluene, ethylbenzene, dimethyl carbonate, methyl n-amyl ketone, cyclohexanone, propylene glycol methyl ether ethyl acetate acid, methyl isoamyl ketone, butyl acetate, ethylene glycol ethyl ether acetate, n-butyl propionate and ethyl acetate.
The high durability flexible rubber to metal adhesive topcoat of the present invention can be prepared and used according to conventional methods in the art, for example, after blending the above improved rubber component with the other components in the system, grinding in a KD mill to a fineness of less than 15 μm to obtain a sample of the heat-vulcanized adhesive of the present invention (i.e., high durability flexible rubber to metal adhesive topcoat) for use.
The second aspect of the invention provides the application of the high-durability flexible rubber-metal adhesive surface coating agent, which is applied to the technical field of seismic isolation and sealing.
The technical scheme provided by the invention has the following beneficial effects:
under the application scene of the shock insulation support, the limit shear deformation of the shock insulation support manufactured by the traditional adhesive product on the market is generally 400-450%, and because the bonding strength between the surface coating agent and the rubber base material is weaker than the strength of the rubber base material or the strength of the bonding interface is weaker than the strength of the rubber body, most of the damaged surface is on the bonding interface of the surface coating adhesive and the rubber when the limit shear deformation test is carried out, so that the application of the shock insulation support is limited to a certain extent. The high-durability flexible rubber metal adhesive surface coating agent is improved by adopting a proper amount of nitrogen-containing compound to obtain improved rubber, so that the deformation result of the surface coating agent under the action of extreme shear is obviously improved, the surface coating agent can generate larger deformation, and the effects of shock absorption and shock insulation are still kept under stronger acting force. Meanwhile, the interface between the rubber and the surface coating agent can be kept complete when the rubber and the surface coating agent are damaged, and the maximum limit deformation of 'no damage to the rubber and no damage to the bonding' is realized in the use process as a result of tearing and damage at the rubber material.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The embodiment provides a high-durability flexible rubber-metal adhesive surface coating agent which comprises the following raw materials in percentage by mass:
the film forming agent is chlorinated butyl rubber and is a 1066-grade product (Mooney viscosity is 38 +/-5, and chlorine content is 1.26 +/-0.08) of Exxon company; the functional rubber is polyvinyl butyral which is a TB-20 product (the viscosity of a 10% ethanol solution is 2800-3800mPa & s, and the content of vinyl butyral is 68-80%) of a company of Yingkou Tianyuan chemical research institute; the filler is carbon black N326; the solvent is xylene; the modified rubber is a reaction type rubber modified by a nitrogen-containing compound, and the preparation method comprises the following steps:
80 parts by mass of the epoxy-terminated nitrile rubber was added to 160 parts by mass of xylene, and the mixture was stirred with a high-speed stirrer at 600RPM for 2 hours to dissolve completely, thereby obtaining a rubber solution having a content of 33.3%. And transferring the solution into a reaction kettle, introducing dry nitrogen to replace air in the reaction kettle for protection, adding 20 parts by mass of p-benzoquinone dioxime, reacting at 60 ℃ for 6 hours, heating to 80 ℃, preserving heat for 0.5 hour, and filtering through a 80-mesh filter screen to obtain the modified rubber. Wherein the epoxy-terminated nitrile rubber is a CHX100 product (the acrylonitrile content is 24 percent, the epoxy functionality is more than or equal to 1.8 percent, and the specific gravity is 0.950) of Beijing DeWaals chemical company Limited.
Example 2
The embodiment provides a high-durability flexible rubber-metal adhesive surface coating agent which comprises the following raw materials in percentage by mass:
the film forming agent is chlorinated butyl rubber and is a 1066-grade product (Mooney viscosity is 38 +/-5, and chlorine content is 1.26 +/-0.08) of Exxon company; the functional rubber is polyvinyl butyral, and is a TB-20 brand product (the viscosity of a 10% ethanol solution is 2800-3800mPa & s, and the content of vinyl butyral is 68-80%) of a company of Yingkou Tianyuan chemical research institute; the filler is carbon black N326; the solvent is xylene; the modified rubber is a reaction type rubber modified by a nitrogen-containing compound, and the preparation method comprises the following steps:
70 parts by mass of epoxy-terminated nitrile rubber is added into 140 parts by mass of xylene, and the mixture is stirred by a high-speed stirrer at the rotating speed of 600RPM for 2 hours to be completely dissolved, so that a rubber solution with the content of 33.3% is obtained. And transferring the solution into a reaction kettle, introducing dry nitrogen to replace air in the reaction kettle for protection, adding 30 parts by mass of p-benzoquinone dioxime, reacting at 60 ℃ for 6 hours, heating to 80 ℃, preserving heat for 0.5 hour, and filtering through a 80-mesh filter screen to obtain the modified rubber. Wherein the epoxy-terminated nitrile rubber is a CHX100 product (the acrylonitrile content is 24 percent, the epoxy functionality is more than or equal to 1.8 percent, and the specific gravity is 0.950) of Beijing DeWaals chemical company Limited.
Example 3
The embodiment provides a high-durability flexible rubber-metal adhesive surface coating agent which comprises the following raw materials in percentage by mass:
the film forming agent is chlorinated butyl rubber and is a 1066-grade product (Mooney viscosity is 38 +/-5, and chlorine content is 1.26 +/-0.08) of Exxon company; the functional rubber is polyvinyl butyral which is a TB-20 product (the viscosity of a 10% ethanol solution is 2800-3800mPa & s, and the content of vinyl butyral is 68-80%) of a company of Yingkou Tianyuan chemical research institute; the filler is carbon black N326; the solvent is xylene; the modified rubber is a reaction type rubber modified by a nitrogen-containing compound, and the preparation method comprises the following steps:
60 parts by mass of the epoxy-terminated nitrile rubber is added to 120 parts by mass of xylene, and the mixture is stirred by a high-speed stirrer at the rotation speed of 600RPM for 2 hours to be completely dissolved, so that a rubber solution with the content of 33.3% is obtained. And transferring the solution into a reaction kettle, introducing dry nitrogen to replace air in the reaction kettle for protection, adding 40 parts by mass of p-benzoquinone dioxime, reacting at 60 ℃ for 6 hours, heating to 80 ℃, preserving heat for 0.5 hour, and filtering through a 80-mesh filter screen to obtain the modified rubber. Wherein the epoxy-terminated nitrile rubber is a CHX100 product (the acrylonitrile content is 24 percent, the epoxy functionality is more than or equal to 1.8 percent, and the specific gravity is 0.950) of Beijing DeWaals chemical company Limited.
Example 4
The embodiment provides a high-durability flexible rubber-metal adhesive surface coating agent which comprises the following raw materials in percentage by mass:
the film forming agent is chlorinated butyl rubber and is a 1066-grade product (Mooney viscosity is 38 +/-5, and chlorine content is 1.26 +/-0.08) of Exxon company; the functional rubber is polyvinyl butyral which is a TB-20 product (the viscosity of a 10% ethanol solution is 2800-3800mPa & s, and the content of vinyl butyral is 68-80%) of a company of Yingkou Tianyuan chemical research institute; the filler is carbon black N326; the solvent is xylene; the modified rubber is a reaction type rubber modified by a nitrogen-containing compound, and the preparation method comprises the following steps:
70 parts by mass of epoxy-terminated nitrile rubber is added into 140 parts by mass of xylene, and the mixture is stirred by a high-speed stirrer at the rotating speed of 600RPM for 2 hours to be completely dissolved, so that a rubber solution with the content of 33.3% is obtained. And transferring the solution into a reaction kettle, introducing dry nitrogen to replace air in the reaction kettle for protection, adding 30 parts by mass of p-benzoquinone dioxime, reacting at 60 ℃ for 6 hours, heating to 80 ℃, preserving heat for 0.5 hour, and filtering through a 80-mesh filter screen to obtain the modified rubber. Wherein the epoxy-terminated nitrile rubber is a CHX100 product (the acrylonitrile content is 24 percent, the epoxy functionality is more than or equal to 1.8 percent, and the specific gravity is 0.950) of Beijing DeWaals chemical company Limited.
Example 5
The embodiment provides a high-durability flexible rubber metal adhesive surface coating agent which comprises the following raw materials in percentage by mass:
the film forming agent is chlorinated butyl rubber and is a 1066-grade product (Mooney viscosity is 38 +/-5, and chlorine content is 1.26 +/-0.08) of Exxon company; the functional rubber is polyvinyl butyral which is a TB-20 product (the viscosity of a 10% ethanol solution is 2800-3800mPa & s, and the content of vinyl butyral is 68-80%) of a company of Yingkou Tianyuan chemical research institute; the filler is carbon black N326; the solvent is xylene; the modified rubber is a reaction type rubber modified by a nitrogen-containing compound, and the preparation method comprises the following steps:
70 parts by mass of epoxy-terminated nitrile rubber is added into 140 parts by mass of xylene, and the mixture is stirred by a high-speed stirrer at the rotating speed of 600RPM for 2 hours to be completely dissolved, so that a rubber solution with the content of 33.3% is obtained. And transferring the solution into a reaction kettle, introducing dry nitrogen to replace air in the reaction kettle for protection, adding 30 parts by mass of p-benzoquinone dioxime, reacting at 60 ℃ for 6 hours, heating to 80 ℃, preserving heat for 0.5 hour, and filtering through a 80-mesh filter screen to obtain the modified rubber. Wherein the epoxy-terminated nitrile rubber is a CHX100 product (the acrylonitrile content is 24 percent, the epoxy functionality is more than or equal to 1.8 percent, and the specific gravity is 0.950) of Beijing DevWako chemical industries, ltd.
Performance test
According to part 3 of GB 20688.3-2006 rubber support, the applicant prepares the surface coating agent sample of the embodiment into a finished product of the vibration isolation support, and then carries out a limit shear deformation performance test on the finished product of the vibration isolation support. Specifically, rubber isolation bearing reduced scale product B type is made to building isolation rubber bearing's standard, and the product diameter is 400mm, 26 layers of rubber layer, rubber gross thickness 130mm, 27 layers of steel sheet layer, steel sheet thickness 1.5mm. The products of Polyton 813 from Shanghai Putong New Material technology, inc. was used as the primer adhesive, and the products in the above examples were used as the top coating, and compared in parallel with Polyton 821, which is a conventional top coating product from Shanghai Putong New Material technology, inc., and two commercially available compositions A (Chemlok 05+6 + 08) and B (Thixon P1 + Megum 5) which are widely used on the market. Wherein comparative example 1 corresponds to a sample having a primer of Polyton 813 and a topcoat of Polyton 821; comparative example 2 corresponds to a sample of commercially available composition a; comparative example 3 corresponds to a sample of commercial composition B. See table 1 below for specific test results.
TABLE 1
| Example/control sample | Ultimate shear deformation results | Form of destruction |
| Comparative example 1 | 433％ | Between rubber and adhesive |
| Example 1 | 455％ | Between rubber and adhesive |
| Example 2 | 496％ | Tearing of rubber |
| Example 3 | 473％ | Tearing of rubber |
| Example 4 | 522％ | Tearing of rubber |
| Example 5 | 487％ | Tearing of rubber |
| Comparative example 2 | 435％ | Between rubber and adhesive |
| Comparative example 3 | 411％ | Between rubber and adhesive |
From the experimental results, the high-durability flexible rubber metal adhesive surface coating agent is obviously superior to the traditional adhesive combination in the limit deformation resistance when being used for bonding a seismic isolation support. The invention can effectively increase the strength and flexibility of the bonding interface, so that the shock insulation support has better shock absorption performance when being deformed by stress, and the durability of the product is greatly improved.
Operations and steps disclosed in embodiments of the invention may be directed to specific aspects of the invention and other steps may be performed in accordance with operations well known to those skilled in the art.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; without conflict, embodiments of the present disclosure and features of the embodiments may be combined with each other to arrive at new embodiments. Various modifications, adaptations, and equivalents may occur to those skilled in the art without departing from the scope and spirit of the present invention.
Claims (10)
1. The high-durability flexible rubber-metal adhesive surface coating agent is characterized by comprising the following raw materials in percentage by mass:
the modified rubber is a reactive rubber modified with a nitrogen-containing compound.
2. The high-durability flexible rubber-metal adhesive top coating agent according to claim 1, wherein the raw material of the nitrogen-containing compound-modified reactive rubber comprises a nitrogen-containing compound and a rubber base material; the nitrogen-containing compound is selected from one or more of nitrobenzene, nitrosobenzene, p-nitrotoluene, p-nitrosotoluene, p-dinitrosobenzene, m-dinitrosobenzene, o-dinitrosobenzene and p-benzoquinone dioxime.
3. The high durability flexible rubber to metal adhesive top coat according to claim 2 wherein said rubber base material is a hydroxyl terminated rubber material and/or an epoxy terminated rubber material.
4. The high durability flexible rubber to metal adhesive topcoat of claim 3, wherein the hydroxyl terminated rubber material and the epoxy terminated rubber material are selected from one or more of hydroxyl terminated nitrile rubber, epoxy terminated nitrile rubber, hydroxyl terminated butyl rubber, epoxy terminated butyl rubber, hydroxyl terminated neoprene, and epoxy terminated neoprene.
5. The high durability, flexible rubber to metal adhesive top coat according to claim 3, wherein the nitrogen containing compound is present in an amount of at least 20% by mass based on the sum of the nitrogen containing compound and the rubber base material; preferably, the content thereof by mass is not more than 40% of the sum of the masses of the nitrogen-containing compound and the rubber base material.
6. The high durability flexible rubber to metal adhesion topcoat as claimed in claim 3, wherein the modified rubber is prepared by a process comprising the steps of:
adding a rubber base material into a benzene solvent, stirring and dissolving to obtain a rubber solution with the solid content of 30-40 w%, adding the rubber solution into a reaction kettle, replacing air in the reaction kettle with nitrogen, adding the nitrogen-containing compound, reacting for 4-8 hours at 55-70 ℃, heating to 75-85 ℃, treating for 20-45 min, cooling to room temperature, and filtering to obtain the rubber-modified polypropylene composite material.
7. The high-durability flexible rubber metal adhesive top-coat agent according to any one of claims 1 to 6, wherein the functional rubber is selected from one or more of chlorosulfonated polyethylene, chlorosulfonated polypropylene, polyisoprene, polyvinyl butyral, and polyvinyl alcohol.
8. The high durability flexible rubber metal adhesive top coating agent according to claim 7 wherein said film forming agent is selected from one or more of chlorinated natural rubber, highly chlorinated neoprene, chlorinated polyethylene, chlorinated polypropylene, chlorinated butyl rubber, brominated butyl rubber.
9. The high durability flexible rubber to metal adhesive topcoat of claim 7, wherein the filler is carbon black.
10. Use of the high durability flexible rubber to metal adhesive top coat according to any of claims 1 to 9 in the field of seismic isolation and sealing technology.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6004425A (en) * | 1995-01-26 | 1999-12-21 | Henkel-Teroson Gmbh | Rubber-based structural white-shell adhesives |
| JP2009007408A (en) * | 2007-06-26 | 2009-01-15 | Sumitomo Rubber Ind Ltd | Rubber composition for adhesion of steel cord and pneumatic tire using the same |
| CN107567486A (en) * | 2015-05-01 | 2018-01-09 | 洛德公司 | Adhesive for rubber bonding |
| CN109337590A (en) * | 2018-09-07 | 2019-02-15 | 上海普力通新材料科技有限公司 | A kind of shock insulation high-damping rubber tailored version Heat vulcanization adhesive |
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2021
- 2021-08-12 CN CN202110925069.5A patent/CN115141579B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6004425A (en) * | 1995-01-26 | 1999-12-21 | Henkel-Teroson Gmbh | Rubber-based structural white-shell adhesives |
| JP2009007408A (en) * | 2007-06-26 | 2009-01-15 | Sumitomo Rubber Ind Ltd | Rubber composition for adhesion of steel cord and pneumatic tire using the same |
| CN107567486A (en) * | 2015-05-01 | 2018-01-09 | 洛德公司 | Adhesive for rubber bonding |
| CN109337590A (en) * | 2018-09-07 | 2019-02-15 | 上海普力通新材料科技有限公司 | A kind of shock insulation high-damping rubber tailored version Heat vulcanization adhesive |
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