WO1986002317A1 - Composition d'immobilisation - Google Patents

Composition d'immobilisation Download PDF

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Publication number
WO1986002317A1
WO1986002317A1 PCT/US1985/001724 US8501724W WO8602317A1 WO 1986002317 A1 WO1986002317 A1 WO 1986002317A1 US 8501724 W US8501724 W US 8501724W WO 8602317 A1 WO8602317 A1 WO 8602317A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
approximately
composition
cyanoacrylate monomer
percent
Prior art date
Application number
PCT/US1985/001724
Other languages
English (en)
Inventor
Travis W. Honeycutt
Original Assignee
Isopedix Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Isopedix Corporation filed Critical Isopedix Corporation
Publication of WO1986002317A1 publication Critical patent/WO1986002317A1/fr

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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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention deals with a method of bonding complementary threaded members such as a nut and bolt by chemical means.
  • compositions of the prior art do not polymerize on the threaded bolt at any location other than beneath the nut. As a result, one is left with a liquid monomer containing composition throughout the length of the bolt which must be wiped from the threads in exposed areas.
  • the above-described prior compositions require a polymerization or set-up time of approximately 30 minutes or longer which can be too long for certain industrial applications.
  • the prior anaerobic compositions generally only perform adequately on threaded members comprised of ferrite surfaces. These compositions do not work well on non- ferrites such as ceramics, stainless steel or plastics, etc.
  • the present invention comprises a method of bonding complementary members.
  • a quantity of a gelled thixotropic ⁇ -cyanoacrylate monomer containing composition is applied and the nut is passed over the threads so coated.
  • the ⁇ -cyanoacrylate monomer containing composition is of such a viscosity and thixotropicity that substantially none of the composition remains on the threaded bolt in areas over which the nut has passed.
  • the composition should possess a reasonably high viscosity, i.e. at least 20,000 cps, and exhibit certain thixotropic properties. Further, the composition should polymerize or harden quickly and yet be capable of some movement in the event that one wishes to remove one member from its threaded counterpart after the hardening agent has polymerized.
  • the hardening agent could be maintained solely at the interface between the threaded members for as one of the members is applied to its complement over threads which have been coated with the hardening agent substantially none of the hardening agent remains on the threads in areas over which the member has passed. It was found that the objects of the present invention could be achieved by providing a thixotropic gel composition containing an ⁇ -cyanoacrylate monomer, a dry colloidal fumed silica, a plasticizer, a stabil ⁇ izer, free radical scavenger, filler and viscosity enhancer.
  • the filler is ideally in the form of fibers or spheres, each taken alone or in combination with the only requirement being that the material comprising the filler be composed of material which is insoluble in and inert to the ⁇ -cyanoacrylate monomer containing composition. . !
  • the fibers and spheres must not have any significant amounts of residual catalyst, such as peroxides, which are used in certain manufacturing techniques for polyolefins etc.
  • residual catalyst such as peroxides
  • polypropylene and polyethylene are preferred materials for the composition of the fibers and spheres.
  • thermally polymerized polypropylene spheres sold under the trade designation Type 6501 from Himmont U.S.A., Inc. and fibers of spun polypropylene sold under the trade designation Type 153 from Hercules Chemical Co. which are produced from thermally polymerized feed stock are most advantageous for use in practicing the present invention.
  • R is a member selected from the group consist ⁇ ing of an alkyl from approximately 1 to 16 carbon atoms; phenyl, cyclohexyl, '' alkoxy, allyl, furfuryl and mixtures thereof.
  • alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and amyl.
  • alkoxy groups include methoxyethyl and ethoxyethyl.
  • ⁇ - cyanoacrylate monomers which are well known in the prior art as adhesives and can be employed herein in an amount between approximately 45.0 to 98.5 percent by weight and more preferably between 71.0 and 94.25 percent by weight and most ideally between approximately 78.0 and 89.0 percent by weight.
  • Added to the ⁇ -cyanoacrylate monomer is a dry colloidal fumed silica, a plasticizer, a stabilizer and free radical scavenger. When proper amounts of these materials are combined, as more fully explained hereinafter, a thixotropic gel composition is achieved which is ideally suited as a hardening agent for the bonding of complementary threaded parts.
  • the present invention be limited to the use of only a dry colloidal fumed silica as the thickening agent. More specifically, this ingredient is preferably a hydrophobic silated silica, as the inclusion of any water will decrease the stability and shelf-life of the composition. It has been found that a product sold under the trademark CAB-0-SIL N 70 TS available from Cabot Corporation is most adequate in practicing the present invention. It is preferable that a plasticizer be employed in the composition for without one, phase separation occurs during storage.
  • Plasticizers for use herein comprise one or more members selected from the group consisting of monofunctional aliphatic esters, such as butyl acetate and butyl cyanoacetate, difunctional aliphatic esters, such as dibutyl phthalate, phosphate esters and phosphonate esters. Although dibutyl and dioctyl phthalate are preferable in carrying out the present invention, one could use 3,4,5-dihydroxybenzoic acid and its esters as taught in U.S. Patent No. 4,139,693 among others known, in the trade. It is preferable that the plasticizers be employed between approximately 0.5 to 5.0 percent by weight and more preferably between 0.75 to 4.0 percent by weight and most preferably between 1.0 to 2.0 percent by weight.
  • certain viscosity modifiers can be included in the formulation.
  • examples of such materials are polyethyl cyanoacrylate or other poly- meric cyanoacrylates, polymethylmethacrylate and cellulose esters. These materials can be incorporated in the composition in amounts between approximately 0.1 to 6.0% by weight. Approximately 3.0% by weight is preferred.
  • a suitable stabilizer is incorporated therein.
  • appropriate stabilizers include sulfur dioxide, hydrogen fluoride, nitrogen oxide, phosphoric acid, phosphorous acid, boron trifluoride, stannic chloride, ferric chloride, sultones and aromatic sulfonic acids.
  • the stabilizing agent should be employed in amounts between approximately 0.0005 to 0.10 percent by weight and more preferably between 0.001 to 0.020 percent by weight and most ideally between approximately 0.007 to 0.010 percent by weight.
  • ⁇ -cyanoacrylates can polymerize via the free radical route, to enhance shelf-life, it is preferable that a free radical scavenger be included in the composition.
  • Such scavengers include hydroquinone, monoethyl ether of hydroquinone, butylated hydroxyanisole, butylated hydroxytoluene and t-buty.l hydroquinone.
  • Hydroquinone is the preferred free radical scavenger for use herein and should be included in amounts between approximately 0.001 to 0.15 parts by weight.
  • ingredients can be combined by virtually any well known technique, it is preferable that means be employed to minimize the amount of water in the system contained e-ither hygroscopically as a contaminant or as an azeotrope. The presence of even small amounts of water will destabilize the composition and greatly reduce its shelf-life. To most efficiently eliminate water in the composition, it is recommended that the various ingredients be added to the composition in a common solvent which could then be removed by vacuum, etc., to eliminate azeotropic water from the final mixture.
  • a suitable solvent should be non-ionic and have a boiling point no higher than approximately 80 ⁇ C.
  • Suitable materials include benzene, toluene, xylene, hexane, chloroform, dichloromethane, acetone, ethyl dichloride and ethyl acetate. These solvents are known to form azeotropes with water and their low boiling points facilitate their removal from the final composition.
  • a flask was fitted with a magnetic stirrer and charged with 500 mis of benzene.
  • Approximately 80.0 parts by weight of the ⁇ -cyanoacrylate monomer was employed in the form of ethoxyethyl ⁇ -cyanoacrylate which was stabilized with approximately 0.003 parts by weight sulfur dioxide and 0.07 parts by weight hydroquinone employed as a free radical scavenger.
  • the viscosity of the composition under shear was regulated by the addition of 0.5 parts by weight polymethylmethacrylate powder as well as 2.0 parts by weight dibutylphthalate as a plasticizer. While being agitated, 6 parts by weight CAB-0-SIL N 70 TS was slowly added.
  • composition was continuously stirred in a flask for approximately 30 minutes whereupon the solvent was stripped off by fitting the flask with dry nitrogen gas and vacuum lines, whereupon the pressure was reduced to approximately 2 mm/Hg while sparging the vessel with dry nitrogen gas to facilitate stripping of the solvent.
  • the composition can be warmed to increase the vapor pressure of the ---solvent.
  • the solvent should be used in amounts between approximately 0.1 to 50 times the weight of the final composition and, more preferably, between approximately 5 to 25 times, and most preferably between 5 and 10 times the weight of the final composition.
  • Example 1 A 3/8"—16 size threaded zinc plated bolt and complementary nut were selected.
  • the composition of Example 1 was liberally applied to the end of the bolt filling approximately 1/4 inch of threads with the hardening composition.
  • the nut was then applied to the bolt and screwed thereon in the normal fashion. While the bolt was being applied, little resistance was noted over and above the normal resistance one would expect during the screwing operation. However, it was observed that virtually none of the hardening composition remained on the threads of the bolt over which the nut had passed and in approximately two minutes, polymerization had taken place to the point where the nut could not be removed from the bolt by ordinary hand manipulation.
  • Example 2 was repeated using nylon nuts and bolts, brass nuts and bolts, aluminum nuts and bolts, as well as cadmium nuts and bolts. In each instance, results similar to those reported for the zinc plated nut and bolt of Example 2 were achieved.
  • the composition is ideally suited as a vehicle for the bonding of two complementary threaded members.
  • the composition is capable of bonding non- threaded members such as metal rivets and threaded members which are applied to solid or non-threaded bodies—such as the application of «a threaded screw to wood or an aluminum screw to sheet metal, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Un procédé permettant de lier des organes filetés complémentaires consiste à appliquer au moins sur certains des filets d'un premier organe sur lequel doit passer un second organe une quantité d'une composition contenant un monomère d'alpha-cyanoacrylate thixotropique gélifié. Ensuite, le second organe est appliqué sur les filets du premier organe sur lesquels la composition contenant le monomère alpha-cyanoacrylate thixotropique gélifié a été appliquée.
PCT/US1985/001724 1984-10-19 1985-09-09 Composition d'immobilisation WO1986002317A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US66270784A 1984-10-19 1984-10-19
US662,707 1984-10-19

Publications (1)

Publication Number Publication Date
WO1986002317A1 true WO1986002317A1 (fr) 1986-04-24

Family

ID=24658855

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1985/001724 WO1986002317A1 (fr) 1984-10-19 1985-09-09 Composition d'immobilisation

Country Status (2)

Country Link
EP (1) EP0198845A1 (fr)
WO (1) WO1986002317A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2585884A (en) * 2019-07-19 2021-01-27 Henkel IP & Holding GmbH Threadlocking system

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022197A (en) * 1957-02-21 1962-02-20 Jedicka Helmut Securing threaded connections
US3178379A (en) * 1961-06-14 1965-04-13 Eastman Kodak Co Method for preparing cyanoacrylate monomer adhesive compositions
US3574135A (en) * 1968-02-20 1971-04-06 Franics R Sampson Production of improved thickened or thixotropic compositions from fluid energy milled colloidal silica
US3769126A (en) * 1970-01-30 1973-10-30 Westinghouse Electric Corp Resinous-microsphere-glass fiber composite
JPS54107993A (en) * 1978-02-10 1979-08-24 Matsumoto Seiyaku Kogyo Kk Alphaacyanoacrylate composition
GB2070622A (en) * 1980-02-29 1981-09-09 Grace W R & Co Silica and fibrous polyolefin thickening agent
US4297160A (en) * 1979-07-16 1981-10-27 Pacer Technology And Resources, Inc. Locking and sealing compositions and methods for their application
JPS59102971A (ja) * 1982-12-03 1984-06-14 Toagosei Chem Ind Co Ltd 接着方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022197A (en) * 1957-02-21 1962-02-20 Jedicka Helmut Securing threaded connections
US3178379A (en) * 1961-06-14 1965-04-13 Eastman Kodak Co Method for preparing cyanoacrylate monomer adhesive compositions
US3574135A (en) * 1968-02-20 1971-04-06 Franics R Sampson Production of improved thickened or thixotropic compositions from fluid energy milled colloidal silica
US3769126A (en) * 1970-01-30 1973-10-30 Westinghouse Electric Corp Resinous-microsphere-glass fiber composite
JPS54107993A (en) * 1978-02-10 1979-08-24 Matsumoto Seiyaku Kogyo Kk Alphaacyanoacrylate composition
US4297160A (en) * 1979-07-16 1981-10-27 Pacer Technology And Resources, Inc. Locking and sealing compositions and methods for their application
GB2070622A (en) * 1980-02-29 1981-09-09 Grace W R & Co Silica and fibrous polyolefin thickening agent
JPS59102971A (ja) * 1982-12-03 1984-06-14 Toagosei Chem Ind Co Ltd 接着方法

Also Published As

Publication number Publication date
EP0198845A1 (fr) 1986-10-29

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