GB2228943A - Cyanoacrylate compositions for bonding porous or non-active substrates - Google Patents
Cyanoacrylate compositions for bonding porous or non-active substrates Download PDFInfo
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- GB2228943A GB2228943A GB9003718A GB9003718A GB2228943A GB 2228943 A GB2228943 A GB 2228943A GB 9003718 A GB9003718 A GB 9003718A GB 9003718 A GB9003718 A GB 9003718A GB 2228943 A GB2228943 A GB 2228943A
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- Prior art keywords
- anion
- composition according
- cyanoacrylate
- cation
- monomer
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- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 229920001651 Cyanoacrylate Polymers 0.000 title claims abstract description 17
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 title description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 239000012954 diazonium Substances 0.000 claims abstract description 3
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 claims abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052752 metalloid Inorganic materials 0.000 claims description 4
- 150000002738 metalloids Chemical class 0.000 claims description 4
- 229910017048 AsF6 Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052781 Neptunium Inorganic materials 0.000 claims description 2
- 239000004825 One-part adhesive Substances 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052774 Proactinium Inorganic materials 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims 1
- 125000005517 carbenium group Chemical group 0.000 claims 1
- -1 ammonium Chemical compound 0.000 abstract description 8
- 239000004830 Super Glue Substances 0.000 abstract description 6
- 125000000129 anionic group Chemical group 0.000 abstract description 6
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002023 wood Substances 0.000 abstract description 6
- 230000000269 nucleophilic effect Effects 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical group OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 4
- 241000287433 Turdus Species 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BMTADKZCRRGXRW-UHFFFAOYSA-N C1C=CC=C1.[CH-]1C=CC=C1.[Co+2] Chemical compound C1C=CC=C1.[CH-]1C=CC=C1.[Co+2] BMTADKZCRRGXRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000533901 Narcissus papyraceus Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 description 1
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Chemical class 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
One-part cyanoacrylate adhesive compositions suitable for bonding porous or non-active surfaces containing a phase transfer catalyst of the formula C<+> A<-> wherein C<+> is a cation other than sulfonium, e.g. ammonium, a quaternary chlorometallate, pyryllium, thiopyryllium, iodonium, phosphonium, metallocenium, or diazonium; and A<-> is an anion of relatively low nucleophilicity which does not initiate polymerisation of the cyanoacrylate monomer, e.g. BF<->4, PF<->6, SbF<->6, SbCl<->4, AsF<->6, SbCl<->6, SnCl<->6, FeCl<->4; or CF<->3SO3. It is believed that upon contact with a surface such as paper or wood the anion A<-> is exchanged for a more nucleophilic anion present on the surface to be bonded. As this other anion is transferred into the composition it initiates anionic polymerisation of the monomer which leads to bonding.
Description
"CYANOACRYLATE COMPOSITIONS FOR BONDING
POROUS OR NON-ACTIVE SUBSTRATES"
This invention relates to cyanoacrylate adhesive compositions which are particularly suitable for bonding porous or non-active surfaces such as wood or paper, surfaces which are acidic or which have been treated with chromates. It is a particular object of the invention to provide a one-part cyanoacrylate composition which is stable on storage but which sets up quickly on application to the surface to be bonded and which therefore can be called an "instant adhesive composition".
In U.S. Patent 4,556,700 Harris et al, we have described the use of various calixarene derivatives as additives for cyanoacrylate compositions.
U.S. Patent 4,460,759 Robins describes a 2-part adhesive system wherein one part comprises an alpha-cyanoacrylate monomer plus stabilizer and the other part is a weakly acidic or weakly basic ionic accelerator compound comprising a cation M and an anion A, the pKa relating to cation M in the equilibrium defined by
being at least about 10, the pKa relating to anion A in the equilibrium defined by
being less than or equal to about 0, and the nucleophilicity constant of anion A being less than about 2 when cation M is an onium cation comprising more than 8 carbons, the nucleophilicity constant being determined relative to methyl iodide.
The cation M may be K+, Na+, Ca+, Li+, Ba++, Ca++, Mg++, Mn++, or an onium cation such as a quaternary ammonium cation e.g. tetraethyl ammonium cation, tetrapropyl ammonium cation, tetrabutyl ammonium cation1 trimethylethyl ammonium cation, dimethyldiethyl ammonium cation, and trimethylbutyl ammonium cation. Examples given of anion A are perchlorate, iodide, bromide, chloride, chlorate, thiocyanate, nitrate, phenylsulfonate, methyl phenyl sulfonate, methylsulfonate, trifluoroacetate, tetrafluoroborate, periodate, triflate, hexafluorophosphate, hexafluoroantimonate and hexafluoroarsenate.
This 2-part adhesive system is said to exhibit suitable cure rates when employed on wooden substrates. However 2-part adhesive systems are inconvenient to use because the accelerator portion must be stored separately and applied as a primer to at least one of the substrate surfaces in a separate operation to the application of the adhesive portion. The Robins Patent contains no teaching about 1-part cyanoacrylate adhesive compositions and it may be deduced that Robins expected that a 1-part composition would cure prematurely and would not have an acceptable storage life.
Japanese Patent Publication No. 58-87170 Toa Gosei Chemical
Industry Co., Limited describes an adhesive composition consisting of a 2-cyanoacrylate and at least one of the following:
(A) a S03 complex of a tertiary amine, and
(B) a sulfonium tetrafluoroborate.
These adhesive compositions are said to have a good storage stability and a rapid adhesion rate on substrates including wood.
However this publication describes only the two narrow groups of accelerators (A) and (B), and does not provide any teaching which would enable one to identify a general class of accelerator compounds.
The sulphonium salt designated UVE1014 by General Electric
Company and iodonium salts have been employed in photocurable epoxy-acrylate compositions. However, these salts need light to effect release of so-formed Lewis acid which brings about cationic cure of the epoxy constituent in the composition and not the acrylate which is cured by free radical agent (photoinitator plus light). This utilisation is described in U.S. Patent 4,156,035 by J. Tsao of W.R.
Grace & Co. Similarly iodonium salts are described in PCT Int.
Application 8501947 090,585 Al 84 by J. Woods and E. Casey of Loctite (Ireland) Limited in photocurable epoxy-acrylate compositions.
However these disclosures do not provide any teaching about the behaviour of sulphonium or iodonium salts in anionic polymerisation of a cyanoacrylate.
The present inventors have now surprisingly found that certain salts or ionic compounds known as phase transfer catalysts can be used in 1-part cyanoacrylate adhesive compositions with good storage life and yet with "instant" adhesive activity upon application to a substrate.
The present invention provides a one-part adhesive composition comprising a cyanoacrylate monomer and a phase transfer catalyst of the formula C+A A wherein C is a cation other than sulfonium, and A- is an anion of low nucleophilicity which does not initiate polymerisation of the cyanoacrylate monomer.
The compositions according to the invention have good storage stability but in contact with a porous or non-active surface such as paper or wood they polymerise very rapidly. Although the present application is not restricted by any theory, it is believed that upon contact with such a surface the soft anion A of the phase transfer catalyst C+ A- is exchanged for a more nucleophilic anion present on the surface to be bonded. As this other anion is transferred into the composition, it initiates anionic polymerisation of the cyanoacrylate monomer and leads to bonding.
The phase transfer catalyst can consist of a metal salt, e.g. a sodium salt complexed with a niacrocyclic compound such as a crown ether or calixarene derivative to render the metal salt soluble in the cyanoacrylate monomer. The compositions according to the invention do not set up in the presence of such a macrocyclic compound, provided that the anion A- is of low nucleophilicity.
The term "low nucleophilicity" will be understood by those skilled in the art. Nucleophilicity is usually defined with respect to a particular substrate (e.g. methyl iodide as in U.S. Patent 4,460,759
Robins). However determinations of nucleophilicity relative to one substrate are not necessarily applicable to another substrate. In the present invention it is sufficient to define "low nucleophilicity" by reference to the behaviour of the anion in the presence of cyanoacrylate monomer i.e. that it is not sufficiently nucleophilic to initiate the anionic polymerisation of the cyanoacrylate.
It will be understood that the adhesive composition may contain an anionic polymerisation inhibitor in conventional amounts of a few parts per million (e.g. up to 10 parts per million). Such inhibitors are normally added to reduce the risk of premature polymerisation of the cyanoacrylate by chance contact with a polymerisation - initiating anionic species, for example on the surface of a manufacturing or storage vessel. However the phase transfer catalysts C+ A of the invention will be present in quantities which are several times greater than those of the inhibitor, so that the inhibitor is unlikely to have any significant effect on the question whether an anion A is or is not of sufficiently high nucleophilicity to initiate polymerisation of the cyanoacrylate monomer.
The anion A may suitably be of the general formula MQe wherein M is a metal or metalloid particularly a transition metal such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, or Cs, a rare earth element including a lanthanide such as Ce, Pr or Nd or an actinide such as Th, Pa, U, Np, or a metalloid such as B, P, As;
Q is a halogen radical;
f = valence of M and is an integer 2-7 inclusive;
e is greater than f and is an integer up to 8.
Particular preferred examples of the anion A of general formula MQe(e f) are BF4, PF6, SbF6, SbCl4,
AsF6, SbCl6, SnCl6, and FeCl4; a further example of the anion A is CF3SO3.
The cation may suitably be:
onium such as ammonium
wherein R1, R2, R3 and R4, which may be the same or different, are H, hydrocarbyl, aryl, or hydrocarbylaryl, provided that at least one of R1, R2, R3 and R4 is other than H;
a quaternary chlorometallate R5 N+ R6 M Clx II
R3" wherein R5 and R6 may be the same or different H or hydrocarbyl and R6 may also be aryl or hydrocarbylaryl, provided that at least one of R5 and R6 is other than H;
M = Fe, Ir, Pt or Au
x = an integer 4-6; pyryllium
wherein R7r R8 and R9 are H, hydrocarbyl, aryl, or hydrocarbylaryl thiopyryl 1 ium
wherein R71 R8 and R9 are as defined above; iodonium
wherein R7 and R8 are as defined above; phosphonium
wherein " R2 R3 and R4 are as defined above; diazonium
Aryl -N2+ carbenium, e.g. trityl or tropylium; metallocenium e.g. ferricenium or cobaltocenium: an alkali metal ion complexed in a macrocycle e.g. a calixarene derivative, a crown ether or polyethylene glycol derivative.
Suitable organometallic complex cations are described in EP 0,109,851 A2 of Minnesota Mining and Manufacturing Company, for example.
The term "hydrocarbyl" as used herein means aliphatic and cycloaliphatic hydrocarbyl. Hydrocarbyl is preferably alkyl or alkenyl, especially having 1-10 carbon atoms, more particularly 4-10 carbon atoms e.g. n-butyl, and may be substituted with one or more halo groups (e.g. chlorine, bromine, fluorine or iodine) or substituted or interrupted by hetero atoms other than nitrogen, particularly oxygen or sulphur.
The phase transfer catalyst is preferably present in an amount of 0.1-5%, particularly 0.5-2% by weight, based on tle cyanoacrylate monomer.
Alpha-cyanoacrylate adhesive compositions are well known and are described, for example in U.S. Patent 4,556,700 Harris et al. While such compositions are composed principally of alpha-cyanoacrylate monomer, the formulation may contain stabilisers, thickeners, adhesion promoters, plasticisers, dyes, heat resistant modifiers, perfumes and such like.
The invention is illustrated in the following Examples:
EXAMPLE 1
To ethyl cyanoacrylate stabilised with 5 parts per million (by weight) methanesulphonic acid were added to the following phase transfer agents at a level of 0.5% by weight based on the monomer:
Phase Transfer Aqent Fixture Time (Secs.) Stabilitv Paper Wood
0 15 300 (CH3)4N+ BF4 5-10 35 r14 days RT
Phase Transfer Agent Fixture Time (Secs.) Stability Paper Wood (CH3CH2CH2CH2)4N+BF4 3 25 1-2 days 820C > 180 days RT (CH3CH2CH2CH2)4N+PF6 10-15 45 N 38 days RT P+ P SbF6 VII 3 15 > 2 days RT 0 VIII VIII 3 45 > 2 days 820C rl l > 180 days RT C S+ < BF4 H3C- If- Ci-(3 AsF6 IX 20 120 > 180 days RT Co+ PF6 X 15 50-70 ) 10 days RT ( (CH3CH2CH2CH2)4N+AuCl4 4 80 ss 2 days RT RT = Room Temperature
EXAMPLE 2
Further tests were carried out on Cyanoacrylate Adhesive
Composition Loctite 495, available from Loctite Corporation, Newington,
Connecticut, U.S.A., using 1% by weight of the additives indicated: :
Fixture Time (Secs.)
Additive Amount Cony PaPer White Deal Stability
O O > 60 240+ (n-C4H9)4N+BF4 1% 7 7 > 6 months RT 2,4-bis-4-allyloxyphenyl-6phenyl pyryllium SbF6 1% 30 20-30 6 months RT
Claims (7)
- CLAIMS 1. A one-part adhesive composition comprising a cyanoacrylate monomer and a phase transfer catalyst of the formula C+ A- wherein C is a cation other than sulfonium, and A- is an anion of relatively low nucleophilicity which does not initiate polymerisation of the cyanoacrylate monomer.
- 2. A composition according to Claim 1 wherein the anion A- is of the general formula MQ-(e-f) wherein M is a metal or metalloid; Q is a halogen radical; f = valence of M and is an integer 2-7 inclusive e is greater than f and is an integer up to 8.
- 3. A composition according to Claim 2 wherein M is selected from: transition metals, rare earth elements, and metalloids.
- 4. A composition according to Claim 3 wherein M is selected from: Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Cs; Ce, Pr, Nd; Th, Pa, U, Np; B, P or As.
- 5. A composition according to Claim 4 wherein the anion A- is selected from BF4, PF6, SbF6, SbC14, AsF6, SbCl6, SnCl6, and FeCl4.
- 6. A composition according to Claim 1 wherein the anion A- is CF3SO3.
- 7. A composition according to Claim 1 wherein the cation C+ is selected from: ammonium; quaternary chlorometallates; pyryllium; thiopyryllium; iodonium; phosphonium; carbenium; metallocenium; diazonium; any of which may be substituted or unsubstituted.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IE71189 | 1989-03-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9003718D0 GB9003718D0 (en) | 1990-04-18 |
| GB2228943A true GB2228943A (en) | 1990-09-12 |
Family
ID=11017145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9003718A Withdrawn GB2228943A (en) | 1989-03-06 | 1990-02-19 | Cyanoacrylate compositions for bonding porous or non-active substrates |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2228943A (en) |
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| US5411998A (en) * | 1992-07-24 | 1995-05-02 | Loctite Limited | Curing anaerobic compositions through thick bondlines |
| WO1998007801A1 (en) * | 1996-08-16 | 1998-02-26 | Loctite (Ireland) Limited | Cyanoacrylate compositions with improved thermal and glass bonding performance |
| WO1998018876A1 (en) * | 1996-10-25 | 1998-05-07 | Henkel Kommanditgesellschaft Auf Aktien | Fluorescent cyanoacrylate adhesive |
| WO2012035112A1 (en) * | 2010-09-15 | 2012-03-22 | Loctite (R&D) Limited | Two-part, cyanoacrylate/cationically curable adhesive systems |
| WO2014042082A1 (en) | 2012-09-11 | 2014-03-20 | 東亞合成株式会社 | 2-cyanoacrylate-based adhesive composition |
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| WO2015137153A1 (en) * | 2014-03-11 | 2015-09-17 | 東亞合成株式会社 | 2-cyanoacrylate adhesive composition |
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1990
- 1990-02-19 GB GB9003718A patent/GB2228943A/en not_active Withdrawn
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| US5411998A (en) * | 1992-07-24 | 1995-05-02 | Loctite Limited | Curing anaerobic compositions through thick bondlines |
| WO1998007801A1 (en) * | 1996-08-16 | 1998-02-26 | Loctite (Ireland) Limited | Cyanoacrylate compositions with improved thermal and glass bonding performance |
| WO1998018876A1 (en) * | 1996-10-25 | 1998-05-07 | Henkel Kommanditgesellschaft Auf Aktien | Fluorescent cyanoacrylate adhesive |
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| JP2014141645A (en) * | 2012-12-26 | 2014-08-07 | Toagosei Co Ltd | 2-cyanoacrylate-based adhesive composition |
| JP2014167097A (en) * | 2013-01-31 | 2014-09-11 | Toagosei Co Ltd | 2-cyanoacrylate-based adhesive composition |
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| WO2015137153A1 (en) * | 2014-03-11 | 2015-09-17 | 東亞合成株式会社 | 2-cyanoacrylate adhesive composition |
| JPWO2015137153A1 (en) * | 2014-03-11 | 2017-04-06 | 東亞合成株式会社 | 2-Cyanoacrylate adhesive composition |
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| Publication number | Publication date |
|---|---|
| GB9003718D0 (en) | 1990-04-18 |
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| Date | Code | Title | Description |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |