Surface insensitive anaerobic adhesive and sealant compositions
View Patent ↗Surface insensitive, storage-stable, single-package liquid anaerobic adhesive and sealant compositions which are substantially free of amines, especially aromatic and tertiary amines, and imides, especially sulfimides such as saccharine and saccharine-type compounds.
1. A method of bonding passive or weakly active substrates that are free of or essentially free of applied or inherent transition metals and without the use of primers or pre-applied activators, said method comprising the steps of
i) applying an anaerobic adhesive composition comprising at least one free radically polymerizable acrylic ester component and a sufficient amount of an activation system for effecting free radical polymerization thereof under anaerobic conditions, said activation system comprising a peroxide free radical initiator and a transition metal metallocene, wherein at least one of the initiator or the metallocene is microencapsulated in a substantially initiator and metallocene impermeable polymer and wherein the microencapsulated initiator or metallocene comprises an encapsulated droplet of a liquid carrier having dispersed or dissolved therein the initiator or metallocene, to at least one of the two surfaces to be bonded,
ii) mating the two surfaces to be bonded in such a way that the mating process causes the release of the microencapsulated component, and
iii) allowing the mated surface to stand to effect cure;
wherein at least one of the surfaces to be bonded is selected from the group consisting of aluminum, zinc, anodic coatings, stainless steel, ceramics and plastics and wherein the cure is effected within 24 hours.
2. The method of claim 1 wherein the carrier is a free radical polymerizable acrylic ester.
3. The method of claim 1 wherein the microencapsulated component is a metallocene.
4. The method of claim 1 wherein the microencapsulated component is a peroxide free radical initiator.
5. The method of claim 1 wherein the free radically polymerizable acrylic ester component comprises one or more acrylic ester monomers, dimers, oligomers, pre-polymers or combinations of any of the foregoing.
6. The method of claim 1 wherein the free radically polymerizable acrylic ester component comprises at least one di- or poly-(meth)acrylate esters.
7. The method of claim 1 wherein the initiator is selected from the group consisting of peroxide initiators and hydroperoxide initiators.
8. The method of claim 7 wherein the initiator is selected from the group consisting of diacyl peroxides, dialkyl peroxides, and hydroperoxides of the formula R 6 (OOH) z wherein R 6 is an alkyl, aryl, or aralkyl hydrocarbon group containing from about 3 to about 12 carbon atoms and z is 1, 2 or 3.
9. The method of claim 1 wherein the metallocene is selected from the group consisting of (i) dicyclopentadienyl metals with the general formula (C 5 H 5 ) 2 M, (ii) dicyclopentadienyl metal halides of the formula (C 5 H 5 ) 2 MX s , where X is halide and s is 1, 2 or 3; (iii) monocyclopentadienyl metal compounds with the general formula C 5 H 5 MR 7 s where s is as defined above and R 7 is CO, NO, a halide group, or an alkyl group, and iv) polymers having incorporated into the polymer chain or grafted thereto a metallocene according to (i), (ii) or (iii), wherein, in each instance, M is a transition metal.
10. The method of claim 9 wherein M is iron.
11. The method of claim 1 wherein the activator system comprises from about 0.2 percent by weight of the initiator and from about 0.05 to about 5 percent by weight metallocene, wherein said weights are based on the total weight of the polymerizable acrylate ester, the initiator and the metallocene, and the weight ratio of metallocene to initiator is from about 0.1:1 to about 5:1.
12. The method of claim 1 further comprising an acid having a pita of from about 1 to about 6, said acid being present in an amount of from about 0.1 to about 1.0 percent by weight based on the total weight of the polymerizable acrylate ester, the initiator, metallocene, and acid.
13. The method of claim 12 wherein the acid is selected from the group consisting of phosphoric acid, methane sulphonic acid and p-toluene sulphonic acid.
14. The method of claim 1 wherein the adhesive is substantially free of amines and imides traditionally associated with the initiation or acceleration of free radical polymerization of acrylic esters.
15. The method of claim 1 wherein the adhesive is substantially free of tertiary amines, aromatic amines and sulfimides.
16. The method of claim 1 wherein the adhesive further comprises an amine or an imide or both that are of a type that has no effect on the speed of free radical polymerization.
17. The method of claim 1 further comprising an amine or an imide or both wherein said amine, imide or combination are present at a level that does not notably affect the speed of free radical polymerization as compared to the same composition without said amine, imide or combination.
18. The method of claim 1 wherein the amount of the initiator or metallocene in the carrier is from 0.2 to 10 weight percent based on the combined weight of the carrier and the initiator or metallocene.
19. The method of dam 1 wherein the substrate or the bonding surface is a plastic.
20. The method of claim 19 wherein the substrate is a polyamide.
21. The method of claim 1 wherein the substrate is a low surface energy thermoplastic.
22. The method of claim 21 wherein the plastic is a polyolefin.
23. The method of claim 21 wherein the plastic is polyethylene or polypropylene.
24. The method of claim 1 wherein the substrate is a passive metal selected from zinc and stainless steel.
25. The method of claim 1 wherein full cure of the anaerobic adhesive is achieved within 6 hours.
26. The method of claim 1 wherein fixture of the substrates is achieved within 8 hours.
27. The method of claim 1 wherein fixture of the substrates is achieved within 3 hours.
28. The method of claim 1 wherein fixture of the substrates is achieved within 1 hour.
29. The method of claim 1 wherein the method involves the bonding of a non-metal surface to a non-metal surface or a metal surface.
30. The method of claim 1 wherein the method involves the bonding of a passive or weakly active metal surface to a passive or weakly active metal surface.